The Chemistry of zirconium/carboxylate clustering process: acidic conditions to promote carboxylate-unsaturated octahedral hexamers and pentanuclear species

The Chemis y o Zi conium/Ca boxyla e Clus e ing P ocess: Acidic
Condi ions o P omo e Ca boxyla e-Unsa u a ed Oc ahed al
Hexame s and Pen anuclea Species
Jon Pascual-Colino, Bena A e xe, Ga ikoi z Beobide, Osca Cas illo,*Ma ia Luz Fidalgo-Mayo,
Ainhoa Isla-López, An onio Luque, Sand a Mena-Gu ié ez, and Sonia Pé ez-Yánez
Ci e This: Ino g. Chem. 2022, 61, 4842−4851
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sıSuppo ing In o ma ion
ABSTRACT: Clus e ing chemis y is a key poin in he design and syn hesis o he
seconda y building uni s ha comp ise me al−o ganic amewo ks (MOFs) based on
g oup IV me als. In his wo k, he fi s s ages o he zi conium-ca boxyla e clus e ing
p ocess in alcohol/wa e mix u es a e s udied in de ail using he monoca boxylic
benzoic and hyd oxybenzoic acids o a oid he polyme iza ion. Mass spec oscopy
measu emen s pe o med on he eac ions e ealed he p esence o hexa- and
pen anuclea species e en a low pH alues and also e idenced he acid−base na u e
and pH dependence o he ans o ma ion be ween bo h species. The con ol on he
chemis y go e ning he equilib ia be ween hese species has allowed us o isola e six
new compounds in he solid s a e. The single-c ys al X- ay diff ac ion analysis
e ealed ha hey a e closely ela ed o he well-known [Z 6(O)4(OH)4(OOC)12]
seconda y building uni ound in many MOFs by emo ing ca boxylic ligands in he
case o he hexame ic species ([Z 6(O)4(OH)4(OOC)8(H2O)8]4+) o by addi ionally
emo ing one o he me al cen e s in he case o he pen ame ic en i ies
([Z 5(O)2(OH)6(OOC)4(H2O)11(alcohol)]6+). Going in de ail, he unsa u a ed hexame ic clus e s exhibi diffe en disposi ions
o hei eigh ca boxyla e ligands in such a way ha he emaining ou ca boxyla e- ee posi ions a e a anged acco ding o a squa e
plana o e ahed al symme y. I should be highligh ed ha he pen ame ic complexes imply an unp eceden ed co e nuclea i y in
zi conium clus e s and hus hei isola ion p o ides a no el building block o he design o me al−o ganic ma e ials.
1. INTRODUCTION
The in e es in he design and p epa a ion o disc e e
polynuclea me al−o ganic en i ies has esu aced
1
no only
in he a eas o classical magne ism
2
and d ug de elopmen
3,4
bu also in he disco e y o new building uni s o design
me al−o ganic amewo ks (MOFs), which show endless
applica ions based on he ailo abili y o hei po osi y.
5
The
key poin o his ascina ing di e si y elies on he modula
building up o hei c ys alline s uc u e based on he
combina ion o o ganic linke s and seconda y building uni s
(SBUs) consis ing mainly o me al nodes o clus e s.
6−8
Un il
ecen ly, no el opologies eme ged basically om he change
o he o ganic linke s, e.g., mo ing om di opic o i opic
linke s. Howe e , his app oach has led o a ne e -ending
inc ease o he complexi y and cos o he b idging ligands
employed o de elop new MOFs.
9−12
The o he cons i uen , he SBUs, seems o be less explo ed,
as usually he syn he ic chemis y elies on he sel -assembled
me al-oxide-hyd oxide polynuclea en i ies and hey appa en ly
show li le a iabili y unde he con en ional syn he ic
condi ions employed o he p epa a ion o hese ma e ials.
13,14
This ac is e iden when analyzing he epo ed s uc u es o
he zi conium/ca boxyla e MOF amily, which a e mos ly
based on he neu al [Z 6(O)4(OH)4(OOC)12]SBU.
Al hough he esul ing sys ems a e bo h chemically and
he mally obus mos ly due o he s eng h o he Z −O
bond,
15,16
he di e si y o he po ous ea u es and opology
elies en i ely on he o ganic linke side. Rega ding he
zi conium/ca boxyla e en i ies, he e a e also some ea ly wo ks
on disc e e Z 6(O)4(OH)4clus e s using small monoca box-
yla es as capping agen s.
17−20
In his con ex , mo e ecen ly, in
si u pai dis ibu ion unc ion (PDF) analysis confi med he
p esence o he hexame ic zi conium clus e in he me al sal
p ecu so /DMF/HCl solu ion p io o he addi ion o he
ca boxylic o ganic ligand.
21
As p e iously s a ed, he no el
membe s o he zi conium MOF amily ely on inc easingly
mo e complex and expensi e polyca boxylic ligands. The e o e,
he e is a g ea in e es in de eloping no el a chi ec u es based
Recei ed: No embe 5, 2021
Published: Ma ch 14, 2022
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on low-cos a oma ic polyca boxylic ligands by modi ying he
ea u es o he SBUs.
22,23
In his sense, a deep esea ch wo k
on he ea ly s ages o he o ma ion o hese polynuclea
en i ies is equi ed.
24
Taking in o accoun hese p emises, we
ha e ho oughly analyzed he o ma ion o disc e e zi conium-
oxide-hyd oxide en i ies in alcoholic media using simple
monoca boxylic benzoa o and hyd oxybenzoa o ligands o
a oid he polyme iza ion ha would hinde his kind o
s udies. A c ucial s age o he se up o he Z −O/OH
polynuclea en i ies esides on he oxygen sou ce om which
hese species eme ge. In his sense, a p ecise con ol o he
amoun o wa e is c ucial o he fi s s eps o he o ma ion o
hese en i ies.
25
On he o he hand, he acidi y o he eac ion
media exe s a s ong influence on he dep o ona ion o he
coo dina ed wa e molecules o affo d b idging hyd oxide and
oxide anions bu also on he eadiness o he ca boxylic ligands
o coo dina e o he me al cen e s.
26
He ein, we epo on se e al disc e e zi conium en i ies
anging om he ubiqui ous hexanuclea [Z 6(μ3-O)4(μ3-
OH)4]12+ co e ob ained by capping some o he linking
posi ions o he SBUs wi h he anionic o ms o he selec ed
monoca boxylic ligands ([Z 6(O)4(OH)4(L)8(H2O)8]4+ whe e
L = benzoa o in 1and 2, 2-hyd oxybenzoa o o salicyla o in 3,
and 3-hyd oxybenzoa o in 4) o a p e iously unknown
pen anuclea [Z 5(μ3-O)2(μ3-OH)2(μ-OH)4]10+ co e
([Z 5(O)2(OH)6(L)4(H2O)11(ROH)]6+ whe e L = benzoa o;
R = E in 5,P in6). In e es ingly, in he case o he o me
oc ahed al-shaped hexanuclea en i ies, he coo dina ion o he
ca boxylic ligands can be ozen in a ca ionic in e media e s a e
in which only some o he a ailable posi ions a e occupied,
lea ing wha can be called a ca boxyla e-unsa u a ed SBU
(Figu e 1).
27
I is wo h men ioning ha zi conium-based
MOFs a e equen ly ca boxyla e-de ec i e (due o andom
linke acancies o due o he es ain s coming om he
opology o he amewo k) bu , in con as o he compounds
epo ed he ein, he cha ge is balanced by he inco po a ion a
hese de ec i e posi ions o smalle monoca boxyla o ligands
( o ma o and ace a o) o by hyd oxide anions.
28,29
I will be
also shown, how he nonco alen in e ac ions coming om he
hyd oxyl-subs i u ed posi ions di ec he a angemen o he
monoca boxylic ligands owa d diffe en symme ies ega ding
he unoccupied ca boxyla o posi ions: hese ha e been placed
in a squa e a angemen o benzoa o (1and 2) and 3-
hyd oxybenzoa o (4) ligands and in a e ahed al one o he 2-
hyd oxybenzoa o (3) ligand.
2. EXPERIMENTAL PROCEDURES
2.1. Chemicals. Zi conium(IV) chlo ide (Z Cl4, Sigma-Ald ich,
anhyd ous, o syn hesis), benzoic acid (C6H6O2, Sigma-Ald ich,
99.5%), salicylic acid (C4H6O3, Sigma-Ald ich, 99%) 3-hyd oxyben-
zoic acid (C4H6O3, Sigma-Ald ich, 99%), absolu e e hanol (C2H6O,
Scha lau), p opanol (C3H8O, PanReac, HPLC g ade). All he
chemicals we e o eagen g ade and used as comme cially ob ained,
excep e hanol ha was dehyd a ed using anhyd ous CaSO4in he
syn hesis o compounds 5and 6.
2.1.1. Syn hesis o Compounds 1,2, and 5.Fo he syn hesis o
hese h ee compounds, a solu ion o 0.3870 g (1.66 mmol) o Z Cl4
dissol ed in 4.8/0.2 mL o e hanol/wa e solu ion was added
d opwise o 8 mL o e hanol solu ion con aining 0.4054 g (3.32
mmol) o benzoic acid. The esul ing colo less solu ion was basified
d opwise wi h wa e un il pH ≈0.0 (2), pH ≈0.5 (1), o le a pH <
−0.2 (5). Reac ion mix u es we e le o e apo a e a oom
empe a u e and colo less single c ys als appea ed a e 3−7 days.
Figu e 1. Schema ic desc ip ion o he unsa u a ed species ob ained in his wo k and hei ela ion wi h he well-known [Z 6(O)4(OH)4(OOC)12]
agmen ound in many MOFs (missing ligands a e colo ed in ligh g ay).
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2.1.1.1. [Z 6(μ3-O)4(μ3-OH)4(μ-OOCC6H5)8(H2O)8]Cl4·E OH·35H2O
(1). Main IR ea u es (cm−1; KB pelle s): 3370 s, 1600s, 1555s,
1525s, 1495s, 14290 s, 1305m, 1180s, 1155m, 1065s, 1025s, 935m,
840w, 720s, 660 s, 465m. 1H MA NMR δ(300 MHz): 7.2 ppm
[a oma ic H], 3.6 ppm [Z -OH2]. 13C MAS NMR δ(300 MHz): 172
ppm [COOH], 132 ppm [C a oma ic].
2.1.1.2. [Z 6(μ3-O)4(μ3-OH)4(μ-OOCC6H5)8(H2O)8]Cl4·15H2O(2).
Main IR ea u es (cm−1; KB pelle s): 3410 s, 1600s, 1555s,
1528 s, 1490s, 1420 s, 1300m, 1180s, 1155m, 1070s, 1020s, 930m,
840w, 720s, 653 s, 460m. 1H MAS NMR δ(300 MHz): 7.2 ppm
[a oma ic H], 3.6 ppm [Z -OH2]. 13C MAS NMR δ(300 MHz): 172
ppm [COOH], 132 ppm [C a oma ic].
2.1.1.3. [Z 5(μ3-O)2(μ3-OH)2(μ-OH)4(μ-OOCC6H5)4(H2O)11(E OH)]-
Cl6·2E OH·10H2O(5). Main IR ea u es (cm−1;KB pelle s):
3420 s, 1622w, 1640w, 1600s, 1560m, 1531 s, 1490m, 1415 s,
1310m, 1175m, 1152w, 1070m, 1018m, 942m, 840w, 720s, 674s,
650m, 524w, 458m. 1H MAS NMR δ(300 MHz): 7.0 ppm [a oma ic
H], 4.3 ppm [Z -OH2], 3.0 ppm [CH2], 0.4 ppm [CH3]. 13C MAS
NMR δ(300 MHz): 172 ppm [COOH], 130 [C a oma ic], 58 ppm
[CH2], 17 ppm [CH3].
2.1.2. Syn hesis o Compound 6.Compound 6was p epa ed by
mixing a solu ion o Z Cl4(0.3870 g, 1.66 mmol) in 2.5/2.5 mL o
e hanol/p opanol mix u e and benzoic acid (0.4054 g, 3.32 mmol) in
8 mL o p opanol. The esul ing colo less solu ion was le a pH <
−0.2. Slow e apo a ion o he eac ion mix u e a oom empe a u e
yielded colo less single c ys als 4 days la e .
2.1.2.1. [Z 5(μ3-O)2(μ3-OH)2(μ-OH)4(μ-OOCC6H5)4(H2O)11(P OH)]-
Cl6·2P OH·11H2O(6). Main IR ea u es (cm−1; KB pelle s):
3410 s, 1622w, 1640w, 1600s, 1560s, 1520 s, 1490s, 1410 s,
1306m, 1180m, 1155w, 1070m, 1020m, 940m, 840w, 720 s, 671s,
650m, 519w, 470m. 1H MAS NMR δ(300 MHz): 7.3 ppm [a oma ic
H], 4.5 ppm [Z -OH2], 2.5 ppm [CH2], −0.5 ppm [CH3]. 13C MAS
NMR δ(300 MHz): 172 ppm [COOH], 131 [C a oma ic], 63 ppm
[CH2], 22 ppm [CH2], 9 ppm [CH3].
2.1.3. Syn hesis o Compounds 3and 4.Fo he syn hesis o hese
compounds, a solu ion o 0.3870 g (1.66 mmol) o Z Cl4dissol ed in
4.8/0.2 mL o e hanol/wa e solu ion was added d opwise o 8 mL o
e hanol solu ion con aining he co esponding ligand, 0.4586 g (3.32
mmol) o 2-hyd oxybenzoic acid o compound 3o 3-hyd ox-
ybenzoic acid o compound 4. The esul ing colo less solu ion was
basified d opwise wi h wa e un il pH ≈0.5 (3)o pH≈1.0 (4).
Reac ion mix u es we e le o e apo a e a oom empe a u e and
colo less single c ys als appea ed a e 3−7 days.
2.1.3.1. [Z 6(μ3-O)4(μ3-OH)4(μ-OOCC6H5O)8(H2O)8]Cl4·28H2O(3).
Main IR ea u es (cm−1; KB pelle s): 3340s, 1622s, 1586s, 1551s,
1484m, 1466s, 1395 s, 1311s, 1244 s, 1160s, 1144s, 1097m, 1026s,
951m, 808s, 755 s, 648m, 475w, 422w. 1H MAS NMR δ(300 MHz):
9.6 ppm [C-OH], 6.5 ppm [a oma ic H], 2.96 ppm [Z -OH2]. 13C
MAS NMR δ(300 MHz): 173 ppm [COOH], 159 ppm [C-OH],
137 and 113 ppm [C a oma ic].
2.1.3.2. [Z 6(μ3-O)4(μ3-OH)4(μ-OOCC6H5O)8(H2O)8]Cl4·27H2O(4).
Main IR ea u es (cm−1; KB pelle s): 3380s, 1608s, 1564s, 1533w,
1493w, 1448s, 1413s, 1302s, 1253s, 1231w, 1160m, 1120s, 1075s,
1000w, 942w, 795s, 764 s, 657 s, 457m. 1H MAS NMR δ(300
MHz): 7.1 ppm [a oma ic H], 4.3 ppm [Z -OH2]. 13C MAS NMR δ
(300 MHz): 172 ppm [COOH], 154 ppm [C-OH], 132 and 120
ppm [C a oma ic].
Rega ding he measu ed pH alues, i he calib a ion o he
elec ode is pe o med in aqueous buffe s, bu he measu emen is
pe o med in a diffe en sol en , he measu ed pH equi es o be
sub ac ed wi h a co ec ion cons an : s
spH = w
spH −δ, whe e s
spH and
w
spH would in his case co espond o he pH o sol en media and
he measu ed pH, while δis a co ec ion cons an . This cons an
depends o he sol en and i can be app oached o −2.54 o e hanol.
The pH alues men ioned in his wo k ha e no been co ec ed and
co espond o w
spH.
30,31
2.2. Cha ac e iza ion. As he c ys als o hese compounds lose
c ys allini y upon hei emo al om he mo he liquo , he pu i y o
he samples was p o ed by FTIR (Fou ie ans o m in a ed
spec oscopy, Table S2), TGA ( he mog a ime ic analysis, Table
S3) and solid s a e NMR (nuclea magne ic esonance) spec os-
copies, oge he wi h powde X- ay diff ac ion (PXRD) expe imen s
pe o med o e samples in oduced in Lindemann ubes al oge he
wi h hei mo he liquo s and using a Debye Sche e ins umen
geome y. Lindemann capilla y PXRD da a we e collec ed using a
Rigaku Sma Lab au oma ic diff ac ome e ope a ing a 40 kV and 50
mA. The 2θscans in ansmission mode we e ob ained wi h pa allel
beam configu a ion (CBO), a capilla y a achmen head, an au oma ic
a enua o , and a 1-D D eX250 de ec o . The diff ac ion da a we e
collec ed in con inuous o a ion, om 3 o 65°s ep size o 0.01°a
0.5°/min scan speed. Rou ine PXRD measu emen s on fil e ed off
samples we e pe o med on a Philips X’PERT diff ac ome e
(equipped wi h Cu-Kα adia ion, λ= 1.5418 Å) o e he ange 5°
<2θ<70°wi h a s ep size o 0.02°, a a iable au oma ic di e gence
sli , and an acquisi ion ime o 2.5 s pe s ep a 293 K.
FTIR spec a o he samples (KB pelle ) we e eco ded a a
esolu ion o 4 cm−1in he 4000−500 cm−1 egion using an FTIR
8400S Shimadzu spec ome e . ATR-FTIR spec a o he compounds
while subme ged in hei mo he liquids we e ob ained using an
a enua ed o al eflec ance (ATR) de ice equipped wi h a special
conca e head a ached o an FTIR 8400S Shimadzu spec ome e .
The mal analysis was pe o med on a METTLER TOLEDO TGA/
SDTA851 he mal analyze in a syn he ic ai (80% N2, 20% O2)flux
o 50 cm3min−1, om oom empe a u e o 800 °C wi h a hea ing
a e o 5 °C min−1and abou 10−20 mg o sample pe un.
Solid s a e NMR measu emen s we e pe o med on powde
samples. High- esolu ion solid-s a e NMR spec a we e eco ded a
298 K on a B uke Ad ance 400 WB spec ome e a 9.4 T, using
100.66 and 400.17 MHz esonance equencies. The 13C expe imen s
we e pe o med wi h c oss-pola iza ion, high powe decoupling, and
magic angle spinning (MAS) configu a ions using a B uke double-
bea ing p obe head and 4 mm zi conia o o s d i en by d y ai . The
MAS a es we e 10 kHz. The Ha mann−Hahn condi ions o 13C
we e ma ched using adaman ane. The ecycle delay was 5 s and he
con ac ime was 2 ms. Chemical shi s we e es ablished using glycine
(Gly) as an ex e nal s anda d (δCO o Gly = 176.5 ppm).
Elec osp ay ioniza ion mass spec ome y (MS) analysis was
conduc ed in an in usion o he eac ion mix u es o a high- esolu ion
mass spec ome e (Synap G2 om Wa e s C oma og afia S.A., ime
o fligh analyze ) a a flow a e o 20 μL/min by an elec osp ay
ioniza ion sou ce in posi i e and nega i e modes. High esolu ion da a
we e acqui ed in scan mode, using a mass ange o 30−1200 u in
esolu ion mode (FWHM ≈20,000) and a scan ime o 0.1 s. The
sou ce empe a u ewasse o120°C and he desol a ion
empe a u e o 350 °C. The capilla y ol age was 2.5 kV (nega i e)
and he cone ol age was 15 V. Ni ogen was used as he desol a ion
and cone gas a flow a es o 600 and 10 L/h, espec i ely. Be o e
analysis, he mass spec ome e was calib a ed wi h a sodium o ma e
solu ion and a leucine enkephalin solu ion was used o he lock mass
co ec ion, moni o ing he ions a a mass- o-cha ge a io (m/z)o
556.2771. All o he acqui ed spec a we e au oma ically co ec ed
du ing acquisi ion based on he lock mass. Fu he de ails a e a ailable
in he Suppo ing In o ma ion.
Single-c ys al XRD da a o s uc u e de e mina ion we e collec ed
on Agilen Technologies Supe no a diff ac ome e s (λMοKα=
0.71073 Å o 1,2,3,5and CuKα= 1.54184 Å o 4and 6). The
da a educ ion was done wi h he C ysAlisP o p og am.
32
C ys al
s uc u es we e sol ed by di ec me hods using he SIR92
33
and
SHELXS
34
p og ams and efined by ull-ma ix leas -squa es on F2
including all eflec ions (WINGX).
35,36
Some c ys al s uc u es o
some o he epo ed compounds show c ys allog aphic diso de in
he posi ions o some o he chlo ide anions and/o he a oma ic ing
o he ca boxylic ligands. The diso de was modeled dis ibu ing he
diso de ed a oms o e wo posi ions and fixing he sum o hei
occupa ion ac o s o one. The c ys al s uc u e o all he compounds
e ealed he p esence o la ge channels in which he sol en molecules
(wa e , e hanol, and p opanol) a e placed. The high diso de ha
sol en molecules p esen p ecluded hei modeling and, as a
consequence, he elec on densi y a he oids o he c ys al s uc u e
was sub ac ed om he eflec ion da a by he SQUEEZE me hod
37
as
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implemen ed in PLATON.
38
De ails o he s uc u e de e mina ion
and efinemen o all compounds a e summa ized in Table S1 in he
Suppo ing In o ma ion.
3. RESULTS AND DISCUSSION
3.1. Mass Spec ome y. To e alua e he fi s s ages o
he clus e ing p ocess, his wo k s a ed wi h he analysis o he
species p esen in solu ion upon he dissolu ion o Z Cl4and
he co esponding benzoic ligand (benzoic, 2-hyd oxybenzoic,
o 3-hyd oxybenzoic acids) in anhyd ous e hanol.
39−43
The
pH alue o he esul ing media was con olled by he addi ion
o wa e o allow a p ecise con ol o he acidi y. This a ia ion
exe s a s ong influence on he species ha a e buil up as
confi med by means o MS. In hese s udies, he appea ances
o pen ame ic and hexame ic zi conium en i ies in which he
ca boxylic ligands a e coo dina ed o he me al cen e s we e
de ec ed. These species we e la e on isola ed in he solid s a e
and hei c ys al s uc u es a e also epo ed in his wo k.
Figu e 2 shows he ESI+mass spec a in he m/z870−950
ange ob ained o he Z Cl4/benzoic acid sys em a diffe en
e y acidic pH condi ions (0, 0.5, and 0.8). All spec a show
wo majo signals cen e ed a m/z884 and 927 wi h a 0.5
spacing o he peaks, indica i e o 2+ cha ge s a es o bo h
species. No species wi h cha ge g ea e han 2+ ha e been
obse ed. The assigned molecula o mula o he hea ie
signal is chemically sound and ag ees well wi h he
Figu e 2. Influence o pH on he ESI+MS spec a signals o he Z Cl4/benzoic acid sys em. Signals belonging o pen ame ic and hexame ic
zi conium species a e iden ified in he m/z: 870−950 ange.
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[Z 6(O)4(OH)4] co e ea u es o he ubiqui ous zi conium-
based hexame ic SBU. Howe e , he benzoa e anions only
pa ially occupy he pe iphe al posi ions a ound his co e in
such a way ha he numbe o ca boxyla e g oups a ached o
he clus e is educed om he expec ed 12 ( he well-known
[Z 6(O)4(OH)4(OOC)12] SBU ound in many MOFs) o 8
p o iding a ca boxyla e-unsa u a ed en i y. This hexame ic
unsa u a ed species inco po a es wo addi ional hyd oxide
anions o p o ide he obse ed 2+ cha ge s a e, and sol en
molecules comple e he coo dina ion sphe e o he clus e .
Simila ly, he signal cen e ed a 884 has been assigned o a
pen ame ic zi conium en i y wi h 2+ cha ge in which 12
sol en molecules, 4 benzoa o ligands, and 4 chlo ides s abilize
a [Z 5(O)2(OH)6] co e. In e es ingly, he signals assigned o
he hexame ic and pen ame ic species show impo an
modifica ions in hei ela i e in ensi ies as a unc ion o pH.
The addi ion o wa e and subsequen dilu ion-d i en mild
basifica ion o he media esul s in a ela i e dec ease o he
in ensi y o he signal belonging o he pen ame ic species,
whe eas ha ela ed o he hexame ic species inc eases
conside ably. This ac can be in e p e ed as an acid−base
equilib ium be ween he wo polynuclea species acco ding o
he chemical eac ion p o ided in Scheme 1.
The o mula ob ained o he pen ame ic species seems o
be closely ela ed o ha o he hexame ic clus e by eleasing
one zi conium a om and losing ou benzoa o ligands, and a
he same ime, educing he amoun o oxides and inc easing
he hyd oxide amoun o keep in a iable he o al amoun o
co e b idging oxide/hyd oxide ligands a eigh . Thus, he e is a
p obable connec ion be ween he zi conium oxide/hyd oxide
species ha can be a ionalized s a ing wi h he well-known
[Z 4(OH)8(sol )16]8+ e ame ic en i y,
44
usually employed as
a comme cial eagen in he o m o i s chlo ide sal ,
45
which in
he p esence o ca boxylic ligands e ol es o a pen anuclea
[Z 5(O)2(OH)6(OOC)4(sol )]6+ species. The g ea e pola -
iza ion effec o he fi h zi conium(IV) cen e p omo es he
dep o ona ion o wo o he hyd oxides o p o ide a wo
oxide/six hyd oxide co e. Upon basifica ion, hese pen anu-
clea en i ies e ol e in o hexanuclea
[Z 6(O)4(OH)4(OOC)8(H2O)]4+ species by he inco po a-
ion o a six h zi conium ha again inc eases he pola iza ion a
he hyd oxide anions leading o a final ou oxide/ ou
hyd oxide co e. Fu he pH inc eases, a o ing he dep o ona-
ion o he ca boxylic ligands, would p obably lead o he
neu al [Z 6(O)4(OH)4(OOC)12] clus e ound as an SBU in
mos o he zi conium-based MOFs.
The same s udies pe o med using 2- and 3-hyd oxybenzoic
acid p o ided simila ou comes bu wi h he p esence o a
g ea e dispe sion o he pen ame ic and hexame ic species due
o a ia ions on he sol en molecules (wa e and e hanol ha
in e change be ween hem). They show he same 2+ m/z
spacing in hei signals and he desc ibed inc ease in he
ela i e in ensi y o he hexame ic species upon basifica ion
(see Sec ion S5 o he Suppo ing In o ma ion). I is wo h
Scheme 1. Acid−Base Equilib ium Go e ning he
T ans o ma ion be ween Pen ame ic and Hexame ic
Species
Figu e 3. Summa y o he polynuclea en i ies p esen in compounds 1−6.
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men ioning ha he basifica ion only implies a change om pH
< 0 o pH ≈1.5.
Fo una ely, hese species we e isola ed in he solid s a e and
a comple e single-c ys al XRD s uc u al cha ac e iza ion was
pe o med. As i will be shown below, he esul s ully
co obo a e he abo e desc ibed conclusion in such a way ha
we we e able o isola e bo h pen ame ic
[Z 5(O)2(OH)6(OOCR)4(H2O)11(HOR′)]Cl6(R: C6H5;R′:
C2H5,C
3H7) and ca boxyla e-unsa u a ed hexame ic
[Z 6(O)4(OH)4(OOCR)8(H2O)8]Cl4(R: C6H5and C6H5O)
compounds as a unc ion o pH.
3.2. C ys al S uc u e o he Polynuclea En i ies. The
c ys al s uc u e o compounds 1−6con ains he p e iously
iden ified disc e e polynuclea en i ies (hexame ic o com-
pounds 1−4; pen ame ic o compounds 5and 6) in which he
hyd oxide o oxide anions a e posi ioned al e na ely in he
cen e o each iangula ace o he me al defining he squa e
py amid o oc ahed on. I means he hexame ic en i y has a
[Z 6(O)4(OH)4]co ewhe eas hepen ame showsa
[Z 5(O)2(OH)6] co e in which he lack o a six h zi conium
a om implies ha he ou hyd oxides poin ing owa d he
acan a e no u he pola ized o p oduce he obse ed
al e na ion o oxides/hyd oxides o he iangula aces (Figu e
3). The ex e nal coo dina ion posi ions o he me al a oms, all
o hem showing a cubic an ip ism geome y, a e occupied by
wa e molecules and ca boxyla e ligands. The hexame ic and
pen ame ic polynuclea en i ies ha e a 4+ and 6+ cha ge,
espec i ely, balanced by chlo ide coun e ions. The coo dina-
ion bond dis ances ound ollow he same end o all he
en i ies. Z −Ooxide dis ances a e always he sho es ones
Figu e 4. S uc u al ea u es o compounds 1(a), 5(b), and 3(c). The b ownish su aces depic ed in he packing images ep esen he olume
occupied by he noncoo dina ed sol en molecules.
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(2.00−2.14 Å), hose in ol ing he oxygen a oms o he
ca boxyla e g oups a e be ween 2.16 and 2.28 Å, whe eas hose
o hyd oxides and wa e molecules a e he longes ones wi h
alues be ween 2.18 and 2.37 Å. The dis ance be ween
adjacen zi conium a oms wi hin he polynuclea en i ies is in
he ange o 3.47−3.54 Å.
All compounds, excep 5and 6, p esen a hexame ic
s uc u e wi h he p e iously desc ibed oc ahed al geome y o
he clus e in which ins ead o he expec ed 12 ca boxylic
ligands, only 8 a e ancho ed o he hexanuclea Z 6(O)4(OH)4
co e (benzoa o in 1,2; 2-hyd oxybenzoa o in 3; and 3-
hyd oxybenzoa o in 4). The emaining coo dina ion posi ions
lacking ca boxyla e g oups (he ein a e : ca boxyla e-unsa u-
a ed posi ions) a e filled wi h wa e molecules. In spi e o he
appa en simila i y be ween compounds 1−4, he a angemen
o he ca boxyla o ligands p o ides a sou ce o isome ism in
hese oc ahed ally shaped polynuclea en i ies. In compounds
1,2(benzoa o), and 4(3-hyd oxybenzoa o), he eigh
ca boxyla e g oups b idge he equa o ial and apical zi conium
a oms. The coo dina ion posi ions loca ed a he equa o ial
edges o he oc ahed on loca ed a e occupied by wa e
molecules affo ding a D4hsymme y. The me al coo dina ion
en i onmen a he apical posi ion consis s o wo oxides, wo
hyd oxides, and ou oxygen a oms om ca boxyla e g oups.
Howe e , he equa o ial zi conium coo dina ion en i onmen
consis s o wo oxides, wo hyd oxides, and wo oxygen a oms
om ca boxyla e g oups and wo wa e molecules.
In con as , compound 3(2-hyd oxybenzoa o ligand) sha es
many o he ea u es o he p e iously desc ibed oc ahed al
clus e s, bu he p esence o he hyd oxyl esidue so close o
he Z 6O4(OH)4co e implies ha posi ioning ou ca boxyla e
g oups a ound he apical zi conium posi ions is now dis a o ed
and ins ead o he p e iously desc ibed D4ha angemen , now
aTdsymme y is achie ed. In his new a angemen , all he
equa o ial edges a e occupied by he ca boxyla o ligands bu
only hal o he equa o ial−apical linking edges a e occupied in
an al e na ed way. Al e na i ely, i can be desc ibed ocusing
on he ca boxyla e lacking edges ha a e a anged in a
e ahed al disposi ion. The e o e, he coo dina ion en i on-
men o he apical zi conium is composed o wo oxide
molecules, wo hyd oxides, wo wa e molecules, and wo
ca boxyla e g oups. On he o he hand, he equa o ial
zi conium coo dina ion en i onmen consis s o wo oxides,
wo hyd oxides, h ee ca boxyla e g oups, and a single wa e
molecule. As usually happens o 2-hyd oxybenzoa e anions
and2-hyd oxybenzoicacidmolecules,anin amolecula
hyd ogen bond be ween he hyd oxyl esidue and one o he
ca boxyla e/ca boxylic oxygen a oms is obse ed.
Compounds 5and 6(wi h benzoa o ligands) consis o
squa e-based py amidal pen ame ic en i ies in which he
absence o he six h zi conium a om is accompanied wi h he
educ ion o he numbe o ancho ed ca boxyla o ligands om
eigh o ou . These ou ca boxyla o ligands a e loca ed
b idging he zi conium a oms in he basal plane wi h he apical
one. The lack o he six h zi conium a om also exe s i s
influence in a lowe pola iza ion capaci y and ins ead o he
ou oxide/ ou hyd oxide composi ion o he polynuclea
co e, a wo oxide/six hyd oxide a io is obse ed. Again, he
emaining posi ions o comple e he eigh coo dina ion
en i onmen o he zi conium a oms a e occupied by wa e
molecules. As a esul , he coo dina ion en i onmen o he
apical zi conium is composed o wo oxides, wo hyd oxides,
and ou oxygen a oms om ou ca boxyla e g oups, whe eas
he coo dina ion en i onmen consis s o one oxide, h ee
hyd oxides, a single ca boxyla e oxygen a om, and h ee wa e
molecules o h ee o he ou basal plane zi conium a oms.
The ou h zi conium in he basal plane shows a diffe en
coo dina ion and ge s coo dina ed o an alcohol molecule
(e hanol in compound 5and p opanol in compound 6).
The e o e, ins ead o ha ing h ee coo dina ed wa e
molecules, i only p esen s wo and he hi d one is eplaced
by he alcohol molecule.
The ca ionic na u e o he polynuclea en i ies implies ha
he ionic in e ac ions wi h he chlo ide coun e ions play a key
ole in di ec ing he c ys al packing o hese compounds. In
compounds 1−3, ionic in e ac ions a e also ein o ced by
s ong hyd ogen bonds es ablished by chlo ide coun e ions
and he b idging hyd oxide anions loca ed in hal o he
iangula aces o he oc ahed ally shaped hexame ic en i ies
(dOH···Cl:2.97−3.26 Å). These chlo ide coun e ions a e
e ahed ally a anged a ound he me al−o ganic clus e s bu
he size diffe ence be ween he big ca ionic en i ies and he
compa a i ely small chlo ide anions make i difficul o achie e
a s ong packing o he c ys al s uc u e and hus equi es a
huge amoun o sol en molecules o p o ide some
cohesi eness o he o e all 3D a chi ec u e (Figu e 4). In
he case o compound 4(3-hyd oxybenzoa o), he hyd oxyl
esidues p o uding om he hexame ic en i ies p o ide a
be e placemen o he chlo ide coun e ions o es ablish
hyd ogen bonding in e ac ions. These ea u es also p o ide an
in e ac ion pa hway be ween he neighbo ing hexame ic
en i ies, which in ol es 3-hyd oxybenzoa o ligands and he
coo dina ed wa e molecules as hyd ogen-bond dono s owa d
he chlo ide coun e ions. Un o una ely, hese in e ac ions
only sp ead along he (101) c ys allog aphic plane and he 3D
cohesi eness equi es again a g ea amoun o sol en
molecules.
The 6+ cha ge o he pen ame ic species implies he
p esence o six chlo ide coun e ions bu only h ee o hem a e
s ongly hyd ogen bonded o he b idging hyd oxide anions.
Two o hem, as p e iously desc ibed o mos o he
hexame ic en i ies, imply he in e ac ion wi h he hyd oxides
placed in he iangula aces and he hi d one occupies a
posi ion close o wha would be he six h zi conium a om i he
clus e would ha e e ol ed owa d he hexame ic en i y. In his
posi ion, he chlo ide anion ac s as an accep o o he hyd ogen
bonding in e ac ions in ol ing he ou b idging hyd oxides
loca ed in he basal plane o he clus e . The emaining h ee
chlo ide coun e ions a e mo e loosely in e ac ing wi h he
clus e h ough he coo dina ed wa e molecules. In ac , one
o hese chlo ides is diso de ed o e wo posi ions indica i e o
he less specific in e ac ions hey es ablish.
In all compounds, sol en molecules accoun o a g ea
po ion o he o al olume o he solid (21.9−33.3%) and
hei loss a e he emo al o he c ys als om he mo he
liquid implies a ans o ma ion o he c ys al s uc u e. In ac ,
hese g ea amoun s o sol en molecules seem o sa u a e he
capaci y o he a oma ic monoca boxylic ligands o es ablish
sup amolecula in e ac ions, and no π-s acking has been
obse ed among hem. Only compound 3exhibi s some
weak double C−H···O hyd ogen bonds in ol ing he 2-
hyd oxibenzoa o ligands om adjacen hexanuclea en i ies.
The fluidi y o he sup amolecula ne wo k in ol ing such a
huge amoun o sol en molecules allows us o isola e
compounds 1and 2, which can be conside ed wo sol a ion
s ages o he same compound, in spi e o he ac ha hey
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exhibi comple ely diffe en uni cell pa ame e s and space
g oup. All in all, al hough he s uc u e collapse makes he
cha ac e iza ion o bulk samples difficul , he homogenei y o
he c ys alline phase was assessed by PXRD analyses o e
samples in oduced in Lindemann ubes, and he s abili y o
he clus e s upon hei emo al om mo he liquo s was
add essed on he basis o solid s a e 1H- and 13C-MAS-NMR
spec oscopy (see he de ails in he Suppo ing In o ma ion).
4. CONCLUSIONS
In summa y, we ha e shown ha he e is plen y o chemis y
s ill o be disco e ed abou he fi s s ages o he zi conium-
ca boxyla e clus e o ma ion. The esul s ende ed he e mus
be unde s ood as ozen images along his p ocess bu also
e eal he oppo uni ies ha a ise om a fine con ol o he
syn he ic condi ions. In ac , among he in e media e species
ha can be ound in he o ma ion o Z -ca boxyla e clus e s, a
s uc u e in which he 12 ca boxyla o ligands b idge he 12
Z −Z edges is he lowes in ene gy acco ding o quan um
mechanical calcula ions.
46
Howe e , his epo does no ake
in o accoun he specific syn he ic condi ions a which hese
en i ies g ow. Ou wo k confi ms ha small modifica ions o
he pH o he media can conside ably affec in he isola ion o
clus e s wi h diffe en nuclea i ies and ca boxyla e-ligand
con en s. In addi ion, species wi h unsa u a ed ca boxyla e
and/o me al posi ions can be a s a ing poin o de elop a
iche chemis y by comple ing hese acancies wi h diffe en
ca boxylic ligands o me al cen e s.
47
In his sense, i has been
possible o isola e zi conium hexame ic en i ies wi h only eigh
ca boxyla e g oups a ached o he clus e and he emaining
ee ou ca boxyla e posi ions a anged in a squa e plana o
e ahed al disposi ion. An unp eceden ed pen ame ic en i y
closely ela ed o he hexame ic ones by he elease o one o
he apical zi conium posi ions is also achie ed, being able o
e eal he acid−base na u e and pH dependence o he
ans o ma ion be ween bo h species.
As a final ema k, i is wo h o men ion ha he esul s
ob ained he e e eal ha in spi e o he ca ionic na u e o he
zi conium clus e s epo ed he ein, hei chemis y shows some
esemblance wi h ha o he anionic polyoxome ala es
(POMs), as he acidi y o he media is also he e a key ac o
in he final nuclea i ies o he esul ing clus e s.
48
Howe e ,
diffe ences a ise om he ac ha he oxida ion s a e o he
zi conium ca ion is no as high as hose displayed by he ypical
addenda me als in POMs (mainly V, Mo, and W). This implies
ha he pola izing capabili y o zi conium is no ha high and
i canno p omo e he comple e dep o ona ion o all he
coo dina ed wa e molecules o affo d an oxide ich en i on-
men able o s abilize hese me al ions. Ins ead o his, he
o ma ion o zi conium-based en i ies wi h highe nuclea i ies
han he classical [Z 4(OH)8(H2O)16]8+ ca ion will equi e he
p esence o coo dina ed ca boxyla e g oups b idging and
holding oge he he me al cen e s.
■ASSOCIATED CONTENT
*
sıSuppo ing In o ma ion
The Suppo ing In o ma ion is a ailable ee o cha ge a
h ps://pubs.acs.o g/doi/10.1021/acs.ino gchem.1c03466.
De ails o spec oscopic da a (FTIR, solid s a e 1H-
NMR and 13C-NMR, and mass spec oscopy), he mog-
a ime ic measu emen s, PXRD da a collec ion, and
c ys allog aphic and s uc u al da a (PDF)
Accession Codes
CCDC 2120125−2120130 con ain he supplemen a y c ys-
allog aphic da a o his pape . These da a can be ob ained
ee o cha ge ia www.ccdc.cam.ac.uk/da a_ eques /ci ,o by
emailing [email p o ec ed], o by con ac ing The
Camb idge C ys allog aphic Da a Cen e, 12 Union Road,
Camb idge CB2 1EZ, UK; ax: +44 1223 336033.
■AUTHOR INFORMATION
Co esponding Au ho
Osca Cas illo −Depa amen o de Química O gánica e
Ino gánica, Facul ad de Ciencia y Tecnología, Uni e sidad
del País Vasco/Euskal He iko Unibe si a ea, UPV/EHU,
Bilbao E-48080, Spain; BCMa e ials, Basque Cen e o
Ma e ials, Applica ions and Nanos uc u es, UPV/EHU
Science Pa k, Leioa E-48940, Spain; o cid.o g/0000-
0002-5614-9301; Email: [email p o ec ed]
Au ho s
Jon Pascual-Colino −Depa amen o de Química O gánica e
Ino gánica, Facul ad de Ciencia y Tecnología, Uni e sidad
del País Vasco/Euskal He iko Unibe si a ea, UPV/EHU,
Bilbao E-48080, Spain
Bena A e xe −Depa amen o de Química O gánica e
Ino gánica, Facul ad de Ciencia y Tecnología, Uni e sidad
del País Vasco/Euskal He iko Unibe si a ea, UPV/EHU,
Bilbao E-48080, Spain; o cid.o g/0000-0002-7373-4596
Ga ikoi z Beobide −Depa amen o de Química O gánica e
Ino gánica, Facul ad de Ciencia y Tecnología, Uni e sidad
del País Vasco/Euskal He iko Unibe si a ea, UPV/EHU,
Bilbao E-48080, Spain; BCMa e ials, Basque Cen e o
Ma e ials, Applica ions and Nanos uc u es, UPV/EHU
Science Pa k, Leioa E-48940, Spain; o cid.o g/0000-
0002-6262-6506
Ma ia Luz Fidalgo-Mayo −Depa amen o de Química
O gánica e Ino gánica, Facul ad de Fa macia, Uni e sidad
del País Vasco/Euskal He iko Unibe si a ea, UPV/EHU,
Vi o ia-Gas eiz E-01006, Spain
Ainhoa Isla-López −Depa amen o de Química O gánica e
Ino gánica, Facul ad de Ciencia y Tecnología, Uni e sidad
del País Vasco/Euskal He iko Unibe si a ea, UPV/EHU,
Bilbao E-48080, Spain
An onio Luque −Depa amen o de Química O gánica e
Ino gánica, Facul ad de Ciencia y Tecnología, Uni e sidad
del País Vasco/Euskal He iko Unibe si a ea, UPV/EHU,
Bilbao E-48080, Spain; BCMa e ials, Basque Cen e o
Ma e ials, Applica ions and Nanos uc u es, UPV/EHU
Science Pa k, Leioa E-48940, Spain
Sand a Mena-Gu ié ez −Depa amen o de Química
O gánica e Ino gánica, Facul ad de Ciencia y Tecnología,
Uni e sidad del País Vasco/Euskal He iko Unibe si a ea,
UPV/EHU, Bilbao E-48080, Spain
Sonia Pé ez-Yánez −BCMa e ials, Basque Cen e o
Ma e ials, Applica ions and Nanos uc u es, UPV/EHU
Science Pa k, Leioa E-48940, Spain; Depa amen o de
Química O gánica e Ino gánica, Facul ad de Fa macia,
Uni e sidad del País Vasco/Euskal He iko Unibe si a ea,
UPV/EHU, Vi o ia-Gas eiz E-01006, Spain
Comple e con ac in o ma ion is a ailable a :
h ps://pubs.acs.o g/10.1021/acs.ino gchem.1c03466
Ino ganic Chemis y pubs.acs.o g/IC A icle
h ps://doi.o g/10.1021/acs.ino gchem.1c03466
Ino g. Chem. 2022, 61, 4842−4851
4849
Au ho Con ibu ions
The manusc ip was w i en h ough con ibu ions o all
au ho s. All au ho s ha e gi en app o al o he final e sion o
he manusc ip .
No es
The au ho s decla e no compe ing financial in e es .
■ACKNOWLEDGMENTS
This wo k has been unded by Eusko Jau la i za/Gobie no-
Vasco (IT1291-19), Uni e sidad del País Vasco/Euskal
He iko Unibe si a ea (p edoc o al ellowship o J.P.C.),
and Minis e io de Ciencia e Inno ación (PID2019-108028GB-
C21). Technical and human suppo p o ided by SGIke
(UPV/EHU, MICINN, GV/EJ, ESF) is also acknowledged.
■REFERENCES
(1) Va dhan, H.; Yusubo , M.; Ve poo , F. Sel -Assembled Me al-
O ganic Polyhed a: An O e iew o Va ious Applica ions. Coo d.
Chem. Re . 2016,306, 171−194.
(2) Mínguez Espalla gas, G.; Co onado, E. Magne ic Func ionali ies
in MOFs: F om he F amewo k o he Po e. Chem. Soc. Re . 2018,47,
533−557.
(3) Sa ke , M.; Jhung, S. H. Z -MOF wi h F ee Ca boxylic Acid o
S o age and Con olled Release o Ca eine. J. Mol. Liq. 2019,296,
No. 112060.
(4) Saman a, S. K.; Isaacs, L. Biomedical Applica ions o Me al
O ganic Polygons and Polyhed a (MOPs). Coo d. Chem. Re . 2020,
410, No. 213181.
(5) Ju, Z.; Liu, G.; Chen, Y. S.; Yuan, D.; Chen, B. F om
Coo dina ion Cages o a S able C ys alline Po ous Hyd ogen-Bonded
F amewo k. Chem. −Eu . J. 2017,23, 4774−4777.
(6) Zhou, H.-C. L.; Je ey, R.; Yaghi, O. M. In oduc ion o Me al −
O ganic F amewo ks. Chem. Re . 2012,112, 673−674.
(7) Eddaoudi, M.; Mole , D. B.; Li, H.; Chen, B.; Reineke, T. M.;
O’Kee e, M.; Yaghi, O. M. Modula Chemis y: Seconda y Building
Uni s as a Basis o he Design o Highly Po ous and Robus Me al-
O ganic Ca boxyla e F amewo ks. Acc. Chem. Res. 2001,34, 319−330.
(8) Yaghi, O. M.; O’Kee e, M.; Ockwig, N. W.; Chae, H. K.;
Eddaoudi, M.; Kim, J. Re icula Syn hesis and he Design o New
Ma e ials. Na u e 2003,423, 705−714.
(9) Chen, T. H.; Popo , I.; Ka ee i i chai, W.; Miljanic
,O.S
. Me al-
O ganic F amewo ks: Rise o he Ligands. Chem. Ma e . 2014,26,
4322−4325.
(10) Qin, J. S.; Yuan, S.; Zhang, L.; Li, B.; Du, D. Y.; Huang, N.;
Guan, W.; D ake, H. F.; Pang, J.; Lan, Y. Q.; Alsalme, A.; Zhou, H. C.
C ea ing Well-De ined Hexabenzoco onene in Zi conium Me al-
O ganic F amewo k by Pos syn he ic Annula ion. J. Am. Chem. Soc.
2019,141, 2054−2060.
(11) Xu, X.; Li, S.; Liu, Q.; Liu, Z.; Yan, W.; Zhao, L.; Zhang, W.;
Zhang, L.; Deng, F.; Cong, H.; Deng, H. Isola ed π-In e ac ion Si es
in Mesopo ous MOF Backbone o Repe i i e and Re e sible
Dynamics in Wa e . ACS Appl. Ma e . In e aces 2019,11, 973−981.
(12) Mallick, A.; Liang, H.; Shekhah, O.; Jia, J.; Mouchaham, G.;
Shku enko, A.; Belmabkhou , Y.; Alsha ee , H. N.; Eddaoudi, M.
Made- o-O de Po ous Elec odes o Supe capaci o s: MOFs
Embedded wi h Redox-Ac i e Cen e s as a Case S udy. Chem.
Commun. 2020,56, 1883−1886.
(13) Cheng, S.; Chen, W.; Zhao, L.; Wang, X.; Qin, C.; Su, Z.
Syn hesis, C ys al S uc u e and Iodine Cap u e o Z -Based Me al-
O ganic Polyhed on. Ino g. Chim. Ac a 2021,516, No. 120174.
(14) Gosselin, A. J.; Rowland, C. A.; Bloch, E. D. Pe manen ly
Mic opo ous Me al-O ganic Polyhed a. Chem. Re . 2020,120, 8987−
9014.
(15) Bai, Y.; Dou, Y.; Xie, L. H.; Ru ledge, W.; Li, J. R.; Zhou, H. C.
Z -Based Me al-O ganic F amewo ks: Design, Syn hesis, S uc u e,
and Applica ions. Chem. Soc. Re . 2016,45, 2327−2367.
(16) Bu ch, N. C.; Jasuja, H.; Wal on, K. S. Wa e S abili y and
Adso p ion in Me al-O ganic F amewo ks. Chem. Re . 2014,114,
10575−10612.
(17) Kickelbick, G.; Schube , U. Oxozi conium Me hac yla e
Clus e s: Z 6(OH)4O4(OMc)12 and Z 4O2(OMc)12 (OMc =
Me hac yla e). Chem. Be ./Recl. 1997,130, 473−478.
(18) Kickelbick, G.; Wiede, P.; Schube , U. Va ia ions in capping
he Z 6O4(OH)4clus e co e: X- ay s uc u e analyses o
[Z 6(OH)4O4(OOC-CH=CH2)10]2(μ-OOC-CH=CH2)4and
Z 6(OH)4O4(OOCR)12(P OH) (R = Ph, CMe=CH2). Ino g. Chim.
Ac a 1999,284,1−7.
(19) Piszczek, P.; Rad ke, A.; G odzicki, A.; Woj czak, A.; Chojnacki,
J. The new ype o [Z 6(μ3-O)4(μ3-OH)4] clus e co e: C ys al
s uc u e and spec al cha ac e iza ion o [Z 6O4(OH)4(OOCR)12]
(R = Bu , C(CH3)2E ). Polyhed on 2007,26, 679−685.
(20) Gao, Y.; Kogle , F. R.; Pe e lik, H.; Schube , U. Ring-opening
me a hesis polyme iza ions wi h no bo nene ca boxyla e-subs i u ed
me al oxo clus e s. J. Ma e . Chem. 2006,16, 3268−3276.
(21) Xu, H.; Somme , S.; B oge, N. L. N.; Gao, J.; I e sen, B. B. The
Chemis y o Nuclea ion: In Si u Pai Dis ibu ion Func ion Analysis
o Seconda y Building Uni s Du ing UiO-66 MOF Fo ma ion. Chem.
−Eu . J. 2019,25, 2051−2058.
(22) Ma shall, R. J.; Fo gan, R. S. Pos syn he ic Modi ica ion o
Zi conium Me al-O ganic F amewo ks. Eu . J. Ino g. Chem. 2016,
2016, 4310−4331.
(23) Ga cía-Raso, A.; Te ón, A.; Roselló, Y.; F on e a, A.; Cas illo,
O.; Beobide, G.; Pé ez-Yánez, S.; Escude o-Adán, E. C.; Fiol, J. J.
Me al Remo al om he Seconda y Building Uni o Bio-MOF-1 by
Adenine N6-Alkyla ion While Re aining he O e all 3D Po ous
Topology. C ys EngComm 2020,22, 4201−4205.
(24) Chen, Z.; Hanna, S. L.; Red e n, L. R.; Alezi, D.; Islamoglu, T.;
Fa ha, O. K. Re icula Chemis y in he Ra ional Syn hesis o
Func ional Zi conium Clus e -Based MOFs. Coo d. Chem. Re . 2019,
386,32−49.
(25) S e n, R. D.; Kingsbu y, R. S.; Pe sson, K. A. Aqueous S abili y
o Zi conium Clus e s, Including he Z (IV) Hexanuclea Hyd olysis
Complex [Z 6O4(OH)4(H2O)24]12+, om Densi y Func ional Theo y.
Ino g. Chem. 2021,60, 15456−15466.
(26) San os-Lo enzo, J.; San José-Velado, R.; Albo, J.; Beobide, G.;
Cas ano, P.; Cas illo, O.; Luque, A.; Pé ez-Yánez, S. A S aigh o wa d
Rou e o Ob ain Zi conium Based Me al-O ganic Gels. Mic opo ous
Mesopo ous Ma e . 2019,284, 128−132.
(27) Pan, L.; Heddy, R.; Li, J.; Zheng, C.; Huang, X. Y.; Tang, X.;
Kilpa ick, L. Syn hesis and S uc u al De e mina ion o a
Hexanuclea Zi conium Glycine Compound Fo med in Aqueous
Solu ion. Ino g. Chem. 2008,47, 5537−5539.
(28) Feng, L.; Pang, J.; She, P.; Li, J.-L.; Qin, J.-S.; Du, D.-Y.; Zhou,
H.-C. Me al−O ganic F amewo ks Based on G oup 3 and 4 Me als.
Ad . Ma e . 2020,32, No. 2004414.
(29) Hu lock, M. J.; Hao, L.; K iegsman, K. W.; Guo, X.; O’Kee e,
M.; Zhang, Q. E olu ion o 14-Connec ed Z 6Seconda y Building
Uni s h ough Pos syn he ic Linke Inco po a ion. ACS Appl. Ma e .
In e aces 2021,13, 51945−51953.
(30) Ba es, R. G.; Paabo, M.; Robinson, R. A. In e p e a ion o PH
Measu emen s in Alcohol-Wa e Sol en s. J. Phys. Chem. 1963,67,
1833−1838.
(31) Gibson, G. T. T.; Mohamed, M. F.; Ne e o , A. A.; B own, R.
S. Po en iome ic Ti a ion o Me al Ions in E hanol. Ino g. Chem.
2006,45, 7891−7902.
(32) Agilen Technologies UK L d. C ysAlisPRO, Ox o d Diff ac ion;
Agilen Technologies UK L d: Ya n on, England.
(33) Al oma e, A.; Casca ano, G.; Giaco azzo, C.; Guaglia di, A.;
Bu la, M. C.; Polido i, G.; Camalli, M. SIRPOW.92 −a P og am o
Au oma ic Solu ion o C ys al S uc u es by Di ec Me hods
Op imized o Powde Da a. J. Appl. C ys allog . 1994,27, 435−436.
(34) Sheld ick, G. M. A Sho His o y o SHELX. Ac a C ys allog .,
Sec . A: Found. C ys allog . 2008,64, 112−122.
(35) Sheld ick, G. M. C ys al S uc u e Re inemen wi h SHELXL.
Ac a C ys allog ., Sec . C: S uc . Chem. 2015,71,3−8.
Ino ganic Chemis y pubs.acs.o g/IC A icle
h ps://doi.o g/10.1021/acs.ino gchem.1c03466
Ino g. Chem. 2022, 61, 4842−4851
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