Va ia ion o Spin-T ansi ion Tempe a u e in he I on(III) Complex
Induced by Di e en Composi ions o he C ys alliza ion Sol en
Published as pa o a C ys al G ow h and Design i ual special issue on Molecula Magne s and Swi chable
Magne ic Ma e ials
I an Nemec,*Lucie Ko ásko á, and Rado an He chel*
Ci e This: C ys . G ow h Des. 2023, 23, 1323−1329
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ACCESS Me ics & Mo e A icle Recommenda ions *
sı Suppo ing In o ma ion
ABSTRACT: We c ys allized he Schi -base i on(III) spin-
c osso e complex [Fe(3,5Cl-L5)(NCSe)] om di e en wo-
componen sol en mix u es con aining me hanol and chlo o o m
(Φ=V(CH3OH)/V(sol en ) = 0.05, 0.25, 0.50, 0.83, and 1.00).
The ob ained c ys alline p oduc s we e cha ac e ized by X- ay
di ac ion, and i was con i med ha hey a e all composed o he
same c ys alline phase, and hey do no con ain any c ys al sol en .
Howe e , signi ican di e ences in magne ic p ope ies we e
obse ed, and he mal hys e esis changed om (in K) 121T↓
and 134T↑ o Φ= 0.05 and 0.25, down o 72T↓and 96T↑ o Φ=
1.00. The c ys al s uc u es o he low-spin and high-spin phases
we e s udied heo e ically and expe imen ally.
The unabili y o he spin-c osso e (SCO) beha io is an
impo an assump ion o e sa ile applica ions o SCO
ma e ials. Bene icially, SCO pa ame e s such as he mal
hys e esis wid h, ansi ion empe a u e (T1/2), coope a i i y
deg ee, cu e ab up ness, and comple eness can be manipu-
la ed by sample modi ica ions. The e ec o he p esence
1−3
and loss
4
o a sol en molecule in he la ice, he selec ion o an
anion,
5,6
as well as he choice o a side subs i uen
6−8
a e well-
known s a egies o modi ying he SCO beha io . Also, me al
dilu ion ep esen s a sophis ica ed app oach o modi ica ion o
he SCO beha io and obse ing o he coope a i i y deg ee
and ansi ion empe a u e o SCO ma e ials. The SCO
beha io can be also uned by a pos syn he ic modi ica ion as
was mani es ed by solid s a e pe o med anion me a hesis.
9
Ou ongoing in e es in he magne ic beha io o Fe(III)
complexes wi h pen aden a e Schi base ligands has b ough
ema kable esul s on dis inc magne ic beha io s o
polymo phs wi hin his class o compounds,
10
o hyd ogen
bonding induced modi ica ion o T1/2.
11
Recen ly, a new epo
on SCO wi h b oad he mal hys e esis obse ed o an Fe(III)
complex wi h a pen aden a e Schi base ligand H23,5Cl-L5
(N,N′-bis(1-hyd oxy-3,5-dichlo o-2-benzyliden)-1,6-diamino-
4-azahexane) has been epo ed by Renz e al. which na u ally
caugh ou a en ion.
12
Complex [Fe(3,5-Cl-L5)(NCSe)] (1)
exhibi s he mally induced SCO wi h 24 K wide he mal
hys e esis (T1/2 = 99↓and 129↑K). F om he compa ison o
he low-spin (LS, S= 1/2) and high-spin (HS, S= 5/2) c ys al
s uc u es, i is appa en ha eo ganiza ion o nonco alen
in e ac ions (H···Cl and Cl···Cl) happens upon spin ansi ion.
This, i signi ican , could explain he obse a ion o he wide
he mal hys e esis. In he o iginal epo ,
12
he au ho s did no
in es iga e his possibili y in g ea e de ail, and he e o e, ou
o iginal mo i a ion o s udying his sys em was o ex ensi ely
heo e ically and expe imen ally in es iga e he LS and HS
c ys al s uc u es o 1.
Fo he p epa a ion o 1we used a p ocedu e simila o ha
in he o iginal epo ,
12
bu ins ead o an ul asonic ba h we
used a s anda d magne ic s i e . The eac ion be ween
[Fe(3,5-Cl-L5)Cl] and KNCSe in pu e me hanol led o
p ecipi a ion o a b own mic oc ys alline powde , which was
il e ed o using a pape il e . Fo he p epa a ion o he
single-c ys als sui able o X- ay di ac ion expe imen s we
used he emaining mo he liquo which was c ys allized
iso he mally. A e se e al days hin needle-like c ys als we e
ob ained. Fi s , we collec ed he di ac ion da a o he HS
s a e (150 K), and hen we a emp ed o measu e he LS s a e
c ys al s uc u e a 90 K as was done in he o iginal epo .
12
To ou su p ise, he measu emen e ealed he c ys al s uc u e
wi h he e y same me al−ligand bond leng hs and uni cell
pa ame e s as was obse ed o he HS phase. Ob iously, his
Recei ed: Decembe 1, 2022
Re ised: Feb ua y 14, 2023
Published: Feb ua y 16, 2023
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© 2023 Ame ican Chemical Socie y 1323
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C ys . G ow h Des. 2023, 23, 1323−1329
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did no ma ch he p e iously epo ed magne ic p ope ies.
12
The e o e, we measu ed he empe a u e dependence o he
magne ic momen (μe /μB) o wo ob ained ac ions, needle-
like c ys als (1_Φ1) and mic oc ys alline powde p ecipi a e
(1_Φ1p). The measu emen s con i med he p esence o SCO
wi h he mal hys e esis o bo h ba ches; howe e , he c i ical
empe a u es and p o iles o magne ic unc ions we e di e en
(Figu e 1). The 1_Φ1ba ch exhibi ed much lowe T1/2 (72↓
and 96↑K, ΔT= 24 K) han 1_Φ1_p (106↓and 129↑K, ΔT
= 23 K, Figu e 1). Powde X- ay di ac ion undoub edly
con i med ha bo h samples we e he same c ys allog aphic
phase iden ical o he HS s uc u e o 1(Suppo ing
In o ma ion, Figu e S6−S7).
Inspi ed by his in iguing inconsis ency, we in es iga ed his
phenomenon in g ea e de ail. F om magne ic measu emen s i
is appa en ha he low T1/2 was obse ed o he ba ch
composed o c ys als which g ew mo e han 5 days, whe eas
he high T1/2 was obse ed o he p ecipi a e. The e o e, one
o he es ed hypo heses was ha di e en c i ical empe a u es
we e ela ed o he c ys allini y o he samples, which is ela ed
o he ime o he c ys alliza ion. In an a emp o p epa e
c ys als, whose c ys alliza ion spans di e en ime pe iods, we
modi ied he composi ion o c ys alliza ion solu ions om pu e
CH3OH o solu ions wi h a g owing po ion o CHCl3. CHCl3
was chosen as he second sol en because i dissol es 1 e y
well; i does no en e he c ys al s uc u e o 1(does no o m
a sol a e) and has a simila boiling empe a u e as CH3OH.
The e o e, i could be expec ed ha he c ys alliza ion o 1will
be go e ned by slow e apo a ion o he sol en mix u e. This
mix u e g adually loses sligh ly mo e CHCl3 han CH3OH
molecules (because o highe apo p essu e o CHCl3), and
hus he solubili y o 1should be con inuously dec easing.
Fou di e en c ys alliza ion mix u es wi h a di e en olume
ac ion Φo CH3OH we e p epa ed (Φ= 0.83, 0.50, 0.25 and
0.05), and he co esponding c ys alline samples (1_Φ0.83,
1_Φ0.50,1_Φ0.25,1_Φ0.05) we e ob ained. In he case o
he solu ions wi h Φ> 0.5 also mic oc ys alline p ecipi a es
1_Φ0.83p (besides al eady p epa ed 1_Φ1_p) we e ob ained
and we e included in o his s udy. The pu i y o all he
p epa ed samples was con i med by X- ay powde di ac ion.
I mus be no ed ha in he case o one o he p ecipi a es
(1_Φ1_p), he p esence o KCl impu i y was de ec ed as his
is a side p oduc o he ligand me a hesis (Cl−ligand was
subs i u ed by KNCSe). We decided no o wash he
p ecipi a es wi h wa e (which would dissol e he impu i y),
because i would in oduce a hi d sol en in o he s udied
sys em. Fu he mo e, he p esence o he diamagne ic KCl
should no a ec he SCO empe a u es.
1c ys allizes as e y hin needle-shaped c ys als. The
symme y o he c ys als is monoclinic wi h he P21/nspace
g oup (see Suppo ing In o ma ion, Table S1). The c ys al
s uc u es o LS and HS phases we e well desc ibed in he
o iginal epo ,
12
and we will no add a new s uc u al
desc ip ion he e.
The bes quali y c ys als we e ob ained o he ba ch
1_Φ0.25. Again, we op ed o measu e he LS and HS c ys al
s uc u es using a selec ed single c ys al om his ba ch. We
moni o ed SCO using di ac ion me hods. The e o e, we
s a ed he single c ys al X- ay di ac ion expe imen s a 140
K, and we collec ed se s o di ac ion da a a selec ed
empe a u es on cooling and also on hea ing. A 116 K (on
cooling), a d ama ic change in he quali y o di ac ions
occu ed as his was he T1/2↓ empe a u e. The c ys al
s uc u e o 1_Φ0.25@↓116K shows me al−ligand (ML)
bond leng hs signi ican ly sho e (Table S2) han obse ed a
highe empe a u es and in e y good ag eemen wi h he LS
s uc u e o 1 epo ed in he o iginal pape .
12
Upon u he
cooling (down o 108 K), nei he he M−L bond leng hs no
he uni cell pa ame e s changed signi ican ly, and he e o e,
we can conclude ha he ull HS →LS spin con e sion
occu ed be ween 116 and 117 K (Figu e 2). Upon hea ing, we
de ec ed he LS →HS ansi ion be ween 133 (LS) and 135 K
(HS s uc u e), whe eas we we e no able o ge easonable
da a om he measu emen a 134 K. We a emp ed o also
measu e ano he SCO he mal cycle, bu he c ys al c acked
upon ano he cooling. He e, we may conclude ha he single
c ys al X- ay di ac ion measu emen s con i med ha
1_Φ0.25 exhibi s he mally induced SCO wi h hys e esis
wide 18 K (i we assume T1/2↑ o be 134 K). This is no in
ag eemen wi h he magne ic da a epo ed in he o iginal
Figu e 1. Tempe a u e dependence o μe /μB o 1_Φ1and 1_Φ1p.
Figu e 2. Tempe a u e dependence o μe /μB o 1_Φ0.25 ( op) and
he empe a u e dependence o he selec ed uni cell pa ame e s as
de e mined om he single c ys al X- ay di ac ion expe imen o
1_Φ0.25 (bo om).
C ys al G ow h & Design pubs.acs.o g/c ys al Communica ion
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pape ,
12
bu i is also no in good ag eemen wi h he magne ic
da a measu ed o 1_Φ1p. O no e he e is ha he coo dina es
o he non-hyd ogen a oms in he HS c ys al s uc u e o
1_Φ1(a 90 K) a e almos iden ical wi h hose de e mined o
1_Φ0.25 (a 130 K, see Suppo ing In o ma ion, Figu e S1)
and hus, he di e ence in T1/2 canno be assigned o changes
in he c ys al s uc u es.
We pe o med magne ic measu emen s o all he p epa ed
ba ches. The esul s showed ha all he samples show
he mally induced spin c osso e (Figu e S2 and Figu e S3).
Rema kably, i is ob ious ha he ba ches p epa ed om he
mix u e wi h he la ges con en o me hanol showed hys e e ic
loops shi ed o lowe empe a u es, whe eas he ba ches om
he highe CHCl3con en had hys e e ic loops shi ed o
highe empe a u es (Figu e S2). The shi o hys e e ic loops
is obse able also be ween 1_Φ0.83 and 1_Φ1; howe e , he
da a o hei p ecipi a es 1_Φ0.83p and 1_Φ1p did no show
a signi ican di e ence in T1/2 (Figu e S3). The hys e e ic
loops o he ba ches wi h he highes CHCl3con en
(1_Φ0.25 and 1_Φ0.05) a e e y simila , and hey exhibi
he highes T1/2. The magne ic beha io o 1_Φ0.25 i s he
empe a u e dependence o he uni cell pa ame e s a he well
(Figu e 2). The obse ed beha io is ep oducible.
The magne ic da a we e analyzed by using an Ising-like
model (ISM) wi h Gaussian dis ibu ion o he coope a i i y
pa ame e de i ed by Boca e al.
13
Wi hin he ISM de ined by
he Hamil onian
=H
2
(1)
he ansi ion be ween wo spin s a es, σ=−1 o LS and σ=
+1 o HS s a es, is go e ned by he ene gy di e ence be ween
HS and LS s a es (Δ) and he coope a i eness o he sys em
(Γ). Such a model can be modi ied o also include he
dis ibu ion o he coope a i i y pa ame e Γin o de o deal
wi h he impe ec ions o he c ys alline/powde samples by
a ying he s anda d de ia ion pa ame e σo he Gaussian
dis ibu ion unc ion. The main ad an age o such a model is
i s abili y o ep oduce he slope o he hys e esis loops, and
hence be e ag eemen wi h he expe imen al da a can be
achie ed. Thus, he magne ic da a we e i ed by a ying Δ,Γ,
e , and σpa ame e s wi hin ISM, and subsequen ly calcula ed
x′HS o gi en empe a u e was used o calcula e o al mola
suscep ibili y as
=x x x(1 )
HS HS HS
(2)
= + +x x x x( ) (1 )
mol HS HS HS HS HS HS
(3)
whe e x HS is he esidual mola ac ion o he HS s a e a a
low empe a u e due o incomple e spin c osso e , and x″HS is
escaled high-spin ac ion calcula ed om ISM esul ing in he
o al high-spin mole ac ion xHS equal o xHS =x″HS +x HS.
The mola suscep ibili y o he HS and LS species was
calcula ed by he Cu ie law. The i ed pa ame e s a e lis ed in
Table S3 and plo ed in Figu e 3 o c ys al samples and in
Figu e S4 o mic oc ys alline p ecipi a es. E iden ly, he e is
small a ia ion o he coope a i i y Γand en opy pa ame e
e wi hin he p epa ed c ys al ba ches o 1, and a ia ions o
T1/2↓and T1/2↑a e mainly due o a a ia ion o Δ.
Fu he mo e, he e is a signi ican inc ease o he dis ibu ion
pa ame e σ o he mic oc ys alline p ecipi a es, Table S3.
We also heo e ically a emp ed o in es iga e he impac o
di e en sol en s on he molecula geome y and he ene gies
o he LS and HS isome o 1using densi y unc ional heo y
(DFT) and u ilizing ORCA 5.0 so wa e.
14
We selec ed h ee
unc ionals based on published benchma k s udies,
15−17
namely, OPBE,
18
2SCAN,
19
and B3LYP*(B3LYP wi h
educed Ha ee−Fock exchange o 15%)
20
and also included
he a om-pai wise dispe sion co ec ion (D4).
21
The op i-
miza ion was done in a acuum, chlo o o m, and me hanol
wi h he C-PCM implici sol a ion model.
22,23
Impac o
Figu e 3. Tempe a u e dependence he high-spin mola ac ion xHS
acco ding o ISM ( op), he ISM pa ame e s (middle), and ansi ion
empe a u es (bo om) o c ys alline samples o 1.
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sol en s is demons a ed o he HS s a e o [Fe(3,5-Cl-
L5)(NCSe)] in Figu e 4. I seems ha OPBE unde es ima es
he Fe−NCSe bond, whe eas B3LYP*and 2SCAN o e -
es ima es he bond leng hs o amino-ni ogen o 3,5-Cl-L5. In
he case o he LS molecula geome ies, OPBE hea ily
unde es ima es all Fe−N bond leng hs (Figu e S5). Mo eo e ,
he e is also signi ican a ia ion in bond leng hs induced by
he implici sol a ion model, which poin s o he impo ance o
in e molecula in e ac ions.
The analysis o he elec onic ene gy di e ences be ween he
HS and LS isome s e ealed posi i e alues o ΔEel =EelHS −
EelLS o all h ee DFT unc ionals, and hus hese unc ionals
p ope ly ound he LS s a e wi h lowe elec onic ene gy (Eel),
Table S4. As he molecula ib a ions ha e a signi ican impac
on he SCO p ope ies, a be e desc ip ion is achie ed wi h
he ene gy di e ence co ec ed by he ze o- empe a u e
ib a ional ene gy om he equency calcula ion, ΔEel+ZPE,
which is depic ed in Figu e 5.
Appa en ly, ΔEel+ZPE is signi ican ly a ec ed by applying he
implici sol a ion model, and bo h B3LYP*and 2SCAN
p o ided easonable alues o he HS-LS sepa a ion. Mo eo e ,
i seems ha a mo e pola sol en like CH3OH ends o
inc ease ΔEel+ZPE, and hus i s abilizes he LS s a e. This is in
con adic ion o he expe imen al inding (Figu e 3 and Table
S3), o which highe Φ(CH3OH) yielded lowe Δand T1/2
alues. We can specula e ha his disc epancy is caused by he
implici sol a ion app oach which canno g asp he e ec o all
in e molecula in e ac ions p ope ly, o he p ope ies o 1in
he solid s a e simply canno be encompassed by such an
app oach a all.
Howe e , i he p esen ed heo e ical calcula ions a e no
decep i e, pe haps i mos likely leads o he conclusion ha
he epo ed phenomenon is no go e ned by he mody-
namics, bu by he kine ics o he c ys al g ow h o 1unde
a ious con en s o chlo o o m and me hanol in c ys allizing
solu ions. Hence, he quali y o he c ys alline ma e ial and
SCO p ope ies a e a ec ed by a sol en mix u e, bu he
sol en molecules do no coc ys allize. One o he possible
app oaches o es his hypo hesis is o co ela e pa ame e s
such as c ys al mosaici y wi h he obse ed magne ic beha io .
The e o e, we decided o p epa e se e al ba ches o 1
c ys allized a di e en c ys alliza ion a es. As was men ioned
abo e, he bes c ys als we e ob ained in he ba ch o
1_Φ0.25. Howe e , he ba ches c ys allized om solu ions
wi h a majo chlo o o m ac ion (Φ0.25 and Φ0.05) ha e
p ac ically he same magne ic p ope ies (Figu e 3). Thus, we
decided o c ys allize 1 om Φ0.5 and Φ0.83 solu ions,
because 1_Φ0.5 and 1_Φ0.83 di e in T1/2↓(114 K o
1_Φ0.5 and 103 K o 1_Φ0.83), and hei spin ansi ion on
Figu e 4. G aphical compa ison o he dono −accep o bond dis ances be ween X- ay da a (do ed lines) and he espec i e DFT me hods
(B3LYP*, OPBE, and 2SCAN) o he high-spin s a e o 1.
Figu e 5. G aphical compa ison he ene gy di e ence co ec ed by
he ze o- empe a u e ib a ional ene gy om he equency
calcula ion ΔEel+ZPE be ween he HS and LS s a es o di e en
DFT me hods applied o 1.
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cooling is s ill accessible using s anda d comme cial c yogenic
de ices (abo e 80 K). Fo p epa a ion o he ba ches, we used
he same eac ion p ocedu es as a e desc ibed in Suppo ing
In o ma ion, bu he mo he liquo s we e c ys allized using
h ee di e en c ys alliza ion a es: as (≈1day), slow (up o 4
days), and e y slow (≥7 days). The majo i y o he used
single c ys als we e ob ained o all he ba ches c ys allized
om Φ0.5 solu ions ega dless o he a e o c ys alliza ion
used. Howe e , also e y slow c ys alliza ion om he Φ0.83
solu ions esul ed in he p oduc ion o a ew sui able single
c ys als.
The c ys al mosaici y was de e mined aking in o consid-
e a ion he esul s o p e ious wo k on mosaici y in SCO
complexes.
24
We se expe imen al condi ions o be as iden ical
as possible o all he in es iga ed specimens. The expe imen
was conduc ed a 150 K, which is well abo e he highes T1/2↓
(Table S3). The da a we e collec ed using ω-scans (wid h 0.5
deg), and he exposi ion ime was adjus ed o each c ys al
based on i s size, aiming o 0.83 Å esolu ion, comple eness
abo e 99%, da a edundancy > 3, and I/σ> 10. As was al eady
men ioned, he c ys als o 1a e e y hin ( ypically ≈0.05 mm
in wo dimensions), needle-like shaped g owing in clumps o
o e lapping specimens, which makes i challenging o
in es iga e he s a is ically ele an numbe o c ys alli es
wi hin a easonable measu emen ime. Thus, we we e capable
o pe o ming measu emen s o a limi ed numbe (14) o
single c ys als. I is impo an o no e ha he as majo i y o
he p epa ed c ys als we e no sui able o single-c ys al
expe imen s, and hus he esul s ob ained only ep esen
hose c ys als ha me he necessa y c i e ia.
A e collec ing each se o da a a 150 K, we de e mined
T1/2↓ o each c ys al by measu ing uni cell pa ame e s s a ing
om 125 K down o 80 K in dec emen s o 5 K. The
occu ence o he SCO phenomenon was eco ded be ween
wo measu ed empe a u e poin s, and he a e age o hese
alues was used o isualiza ion pu poses. The T1/2↓ alue o
c ys als ha emained in he high spin phase a 80 K was se o
70 K o isualiza ion pu poses. The dis ibu ion o he
de e mined T1/2↓ alues is shown (Figu e 6A). The esul s
suppo ed ou hypo hesis ha he speed o c ys alliza ion
a ec s he quali y o c ys als and he T1/2↓ alue. C ys als
c ys allized in he ” as ” and “slow” modes showed T1/2↓ alues
abo e 100 K. C ys als ha c ys allized “ e y slowly” showed
Figu e 6. Plo o T1/2↓ e sus c ys alliza ion a e (A). The colo ed boxes a e used o highligh he c ys alliza ion a e, wi h a ligh e colo indica ing
slowe c ys alliza ion. The plo s o Rin s T1/2↓(B), e3 s T1/2↓(C), and ea g s T1/2↓(D). The alue o ea g was calcula ed as he a i hme ic a e age
o componen s e1,e2, and e3. In all plo s, he T1/2↓ alue o c ys als ha emained in he high spin phase down o 80 K was assigned as 70 K o
isualiza ion pu poses.
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C ys . G ow h Des. 2023, 23, 1323−1329
1327

T1/2↓ alues below 90 K wi h mos o hem ha ing T1/2↓e en
below 80 K.
The esul s o he X- ay di ac ion measu emen s we e
e alua ed in he C ysAlisP o so wa e.
25
As a i s indica ion o
he c ys al quali y, we inspec ed he equi alency o symme y
equi alen e lec ions (Rin ) in he s udied c ys als. The e is no
s ong co ela ion be ween T1/2↓and Rin , bu appa en ly, he
c ys als wi h lowe T1/2↓ alues end o ha e la ge Rin and ice
e sa (Figu e 6B).
The C ysAlisP o so wa e p o ides he mosaici y in h ee
di ec ions (e1,e2, and e3) by i ing a Gaussian unc ion o he
peak.
26,27
Al hough hese pa ame e s do no measu e he
mosaici y di ec ly, a ia ions in he alues o e1,e2, and e3can
indica e changes in he mosaici y o he s udied c ys als and
hus hei quali y.
28
Some au ho s only use he e3pa ame e
due o i s co ela ion wi h mosaici y alues ob ained om
o he da a in eg a ion me hods.
26
The esul s e ealed ha he
e2componen a ied sligh ly among he measu emen s (0.76−
0.96°), while la ge a ia ions we e obse ed o e1(0.75−
2.61°) and e3(0.71−1.66°). As pe p e ious epo s, o
e alua ion o mosaici y, we conside ed he alues o e3and he
a i hme ic a e age (ea g)
29
o all h ee componen s e1,e2, and e3
(Figu e 6C−D, Table S5). As wi h Rin , he esul s o ea g and
e3did no show a s ong linea co ela ion; howe e , c ys als
wi h highe T1/2↓ alues end o ha e lowe alues o eand e3
and ice e sa.
In summa y, o he bes o ou knowledge, such an
unp eceden ed sol en -induced a ia ion o SCO spin-
ansi ion empe a u e as was discussed o 1has no been
epo ed ye . We showed ha he di e en c ys alliza ion a es
p oduced c ys als exhibi ing di e en SCO c i ical empe -
a u es. Ve y slow c ys alliza ion (≥7 days) o he Φ0.5 and
Φ0.83 solu ions esul ed in o c ys als exhibi ing low SCO
c i ical empe a u es (T1/2↓< 90 K), while as e c ys alliza ion
(sho e han 4 days) led o la ge T1/2↓ alues (>100 K). The
pe o med di ac ion expe imen s indica e ha c ys als wi h
low T1/2↓ alues end o ha e la ge mosaici y pa ame e s and
Rin , and hus hey a e o lowe quali y han hose wi h la ge
T1/2↓ alues.
■ASSOCIATED CONTENT
*
sı Suppo 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.cgd.2c01411.
Syn hesis, c ys allog aphic da a, magne ic measu emen s,
DFT calcula ion de ails, and powde di ac ion pa e ns
(PDF)
Accession Codes
CCDC 1909057 and 2223462−2223463 con ain he supple-
men 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 s
I an Nemec −Cen al Eu opean Ins i u e o Technology, B no
Uni e si y o Technology, 61200 B no, Czech Republic;
Depa men o Ino ganic Chemis y, PalackyUni e si y,
77900 Olomouc, Czech Republic; o cid.o g/0000-0003-
3231-7849; Email: [email p o ec ed]
Rado an He chel −Depa men o Ino ganic Chemis y,
PalackyUni e si y, 77900 Olomouc, Czech Republic;
o cid.o g/0000-0001-8262-4666;
Email: [email p o ec ed]
Au ho
Lucie Ko ásko á −Cen al Eu opean Ins i u e o Technology,
B no Uni e si y o Technology, 61200 B no, Czech Republic;
o cid.o g/0000-0003-4825-3616
Comple e con ac in o ma ion is a ailable a :
h ps://pubs.acs.o g/10.1021/acs.cgd.2c01411
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 inal e sion o
he manusc ip .
No es
The au ho s decla e no compe ing inancial in e es .
■ACKNOWLEDGMENTS
The au ho s (I.N. and R.H.) acknowledge inancial suppo
om ins i u ional sou ces o he Depa men o Ino ganic
Chemis y and PalackyUni e si y Olomouc, Czech Republic.
We also acknowledge he CzechNanoLab Resea ch In a-
s uc u e suppo ed by MEYS CR (LM2018110) o he
measu emen o some o he magne ic da a. I.N. is g a e ul o
Jakub Wojciechowski o discussions abou mosaici y e alua-
ion in C ysAlisP o so wa e.
■REFERENCES
(1) Ba i, R. A.; Si a die e, J. Low-Spin-High-Spin T ansi ions in
T ansi ion-Me al-Ion Compounds. Phys. Re . B 1972,5(11), 4466−
4471.
(2) Wajn lasz, J. E ude de La T ansi ion “Low Spin”-“High Spin”
Dans Les Complexes Oc aed iques d’ion de T ansi ion. Phys. s a us
solidi 1970,40 (2), 537−545.
(3) Boca, R.; Line , W. Is The e a Need o New Models o he Spin
C osso e ? In Molecula Magne s Recen Highligh s; Sp inge Vienna:
Vienna, 2002; pp 83−100.
(4) Shaki o a, O. G.; La eno a, L. G.; Ku a ’e a, N. V.; Naumo ,
D. Y.; Dale skii, V. A.; Sheludyako a, L. A.; Log inenko, V. A.;
Vasile skii, S. F. Spin C osso e in I on(II) Complexes wi h
T is(Py azol-1-Yl)Me hane. Russ. J. Coo d. Chem. 2010,36 (4),
275−283.
(5) Halc ow, M. A. S uc u e:Func ion Rela ionships in Molecula
Spin-C osso e Complexes. Chem. Soc. Re . 2011,40 (7), 4119.
(6) Roubeau, O. T iazole-Based One-Dimensional Spin-C osso e
Coo dina ion Polyme s. Chem. - A Eu . J. 2012,18 (48), 15230−
15244.
(7) A cis-Cas íllo, Z.; Zheng, S.; Siegle , M. A.; Roubeau, O.;
Bedoui, S.; Bonne , S. Tuning he T ansi ion Tempe a u e and
Coope a i i y o Bapbpy-Based Mononuclea Spin-C osso e Com-
pounds: In e play be ween Molecula and C ys al Enginee ing. Chem.
- A Eu . J. 2011,17 (52), 14826−14836.
(8) Fel ham, H. L. C.; Johnson, C.; Ellio , A. B. S.; Go don, K. C.;
Alb ech , M.; B ooke , S. “Tail” Tuning o I on(II) Spin C osso e
Tempe a u e by 100 K. Ino g. Chem. 2015,54 (6), 2902−2909.
(9) Askew, J. H.; Shephe d, H. J. Pos -Syn he ic Anion Exchange in
I on(II) 1,2,4-T iazole Based Spin C osso e Ma e ials ia
Mechanochemis y. Dal . T ans. 2020,49 (9), 2966−2971.
(10) K uge , C.; Augus ín, P.; Dlhán, L.; Pa lik, J.; Moncol’, J.;
Nemec, I.; Boca, R.; Renz, F. I on(III) Complexes wi h Pen aden a e
Schi -Base Ligands: In luence o C ys al Packing Change and
Pseudohalido Coligand Va ia ions on Spin C osso e . Polyhed on
2015,87, 194−201.
C ys al G ow h & Design pubs.acs.o g/c ys al Communica ion
h ps://doi.o g/10.1021/acs.cgd.2c01411
C ys . G ow h Des. 2023, 23, 1323−1329
1328
(11) Nemec, I.; He chel, R.; T á nícek, Z. The Rela ionship
be ween he S eng h o Hyd ogen Bonding and Spin C osso e
Beha iou in a Se ies o I on(III) Schi Base Complexes. Dal . T ans.
2015,44 (10), 4474−4484.
(12) Rajnak, C.; Mico á, R.; Moncol, J.; Dlhán, L.; K uge , C.; Renz,
F.; Boca, R. Spin-C osso e in an I on(III) Complex Showing a B oad
The mal Hys e esis. Dal on T ans. 2021,50 (2), 472−475.
(13) Boca, R.; Boca, M.; Dlhán, L.; Falk, K.; Fuess, H.; Haase, W.;
Ja osciak, R.; Papánko á, B.; Renz, F.; V bo á, M.; We ne , R. S ong
Coope a i eness in he Mononuclea I on(II) De i a i e Exhibi ing
an Ab up Spin T ansi ion abo e 400 K. Ino g. Chem. 2001,40 (13),
3025−3033.
(14) Neese, F. So wa e Upda e: The ORCA P og am Sys em -
Ve sion 5.0. WIREs Compu . Mol. Sci. 2022,12, e1606.
(15) Ci e a, J.; Ruiz, E. Assessmen o he SCAN Func ional o
Spin-S a e Ene gies in Spin-C osso e Sys ems. J. Phys. Chem. A 2020,
124 (24), 5053−5058.
(16) Ci e a, J.; Via-Nadal, M.; Ruiz, E. Benchma king Densi y
Func ional Me hods o Calcula ion o S a e Ene gies o Fi s Row
Spin-C osso e Molecules. Ino g. Chem. 2018,57 (22), 14097−
14105.
(17) Siig, O. S.; Kepp, K. P. I on(II) and I on(III) Spin C osso e :
Towa d an Op imal Densi y Func ional. J. Phys. Chem. A 2018,122
(16), 4208−4217.
(18) Pe dew, J. P.; Bu ke, K.; E nze ho , M. Gene alized G adien
App oxima ion Made Simple. Phys. Re . Le . 1996,77 (18), 3865−
3868.
(19) Fu ness, J. W.; Kaplan, A. D.; Ning, J.; Pe dew, J. P.; Sun, J.
Accu a e and Nume ically E icien 2 SCAN Me a-Gene alized
G adien App oxima ion. J. Phys. Chem. Le . 2020,11 (19), 8208−
8215.
(20) Reihe , M. Theo e ical S udy o he Fe(Phen)2(NCS)2 Spin-
C osso e Complex wi h Repa ame ized Densi y Func ionals. Ino g.
Chem. 2002,41 (25), 6928−6935.
(21) Caldeweyhe , E.; Ehle , S.; Hansen, A.; Neugebaue , H.;
Spiche , S.; Bannwa h, C.; G imme, S. A Gene ally Applicable
A omic-Cha ge Dependen London Dispe sion Co ec ion. J. Chem.
Phys. 2019,150 (15), 154122.
(22) Ga cia-Ra és, M.; Neese, F. E ec o he Solu e Ca i y on he
Sol a ion Ene gy and I s De i a i es wi hin he F amewo k o he
Gaussian Cha ge Scheme. J. Compu . Chem. 2020,41 (9), 922−939.
(23) Ba one, V.; Cossi, M. Quan um Calcula ion o Molecula
Ene gies and Ene gy G adien s in Solu ion by a Conduc o Sol en
Model. J. Phys. Chem. A 1998,102 (11), 1995−2001.
(24) Lakhlou i, S.; Tailleu , E.; Guo, W.; Le Gac, F.; Ma chi ie, M.;
Lemée-Cailleau, M.-H.; Chas ane , G.; Guionneau, P. Mosaici y o
Spin-C osso e C ys als. C ys als 2018,8(9), 363.
(25) C ysAlisP o, 1.171.42.49; Rigaku Ox o d Di ac ion, 2020.
(26) Ha ison, K.; Wu, Z.; Jue s, D. H. A Compa ison o Gas S eam
Cooling and Plunge Cooling o Mac omolecula C ys als. J. Appl.
C ys allog . 2019,52 (5), 1222−1232.
(27) Kabsch, W. In eg a ion, Scaling, Space-G oup Assignmen and
Pos -Re inemen . Ac a C ys allog . Sec . D Biol. C ys allog . 2010,66
(2), 133−144.
(28) Madsen, S. R.; O e gaa d, J.; S alke, D.; I e sen, B. B. High-
P essu e Single C ys al X-Ray Di ac ion S udy o he Linea Me al
Chain Compound Co3(Dpa)4B 2·CH2Cl2. Dal . T ans. 2015,44
(19), 9038−9043.
(29) Fa ley, C.; Bu ks, G.; Siege , T.; Jue s, D. H. Imp o ed
Rep oducibili y o Uni -Cell Pa ame e s in Mac omolecula C y-
oc ys allog aphy by Limi ing Dehyd a ion du ing C ys al Moun ing.
Ac a C ys allog . Sec . D Biol. C ys allog . 2014,70 (8), 2111−2124.
C ys al G ow h & Design pubs.acs.o g/c ys al Communica ion
h ps://doi.o g/10.1021/acs.cgd.2c01411
C ys . G ow h Des. 2023, 23, 1323−1329
1329
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