Scan o ge mo e De ails
Po phyS uc
S uc u alAnalysiso Po phy inoids
Con o ma ional Analysis o a a ie y o Po phy inoids
The Con o ma ional Pe iodic Table o Co oles
Coppe -Co oles a e SUPERSADDLED!
Con o ma ional Analysis o a a ie y o Po phy inoids
While he non-plana displacemen s o Po phy ins and hei consequences on
bo h chemical and physical p ope ies we e in es iga ed using he NSD Me hod,
such a me hod did no exis o o he po phy inoids, like Co oles, o a long ime.
Wi h Po phyS uc such analyses a e possible o Po phy ins, Co oles,
No co oles, Co phycenes and Po phycenes and hei s uc u al ela i es. A
Minimal and Ex ended Basis o e e ence s uc u es is a ailable o each o hose
mac ocyclic ypes. In mos cases he minimal basis is su icien o desc ibe he
con o ma ion.
The Con o ma ional Pe iodic Table o Co oles
Coppe -Co oles a e SUPERSADDLED!
Chem. Eu . J. 2021
Jens K umsieck, Ma in B ö ing
TU B aunschweig, Ins i u ü Ano ganische und Analy ische Chemie
# o s uc u es
G oup
s
s
Clus e analysisusing SNE o dimensionali y educ ion
Sys ema ic s udies o he s uc u es o co oles known om he li e a u e a e now possible. Fi s analyses indica e
dependencies on cen al a om, subs i u ion pa e n and non-innocence cha ac e is ics. Doming,saddling and u ling modes
a e o en ound side by side, and wa ing modes a e mo e salien han wi hin po phy in s uc u es. The o e all commonnes
o modes ollows hei ene ge ic o de in he calcula ed e e ence. Fo compa abili y, he analyses we e pe o med wi h he
ex ended basis and a composi e alue (comp) was calcula ed o each o he 6 modes.
Supe saddling is a phenomenon exclusi e o
coinage me al complexes (mos ly Cu). These
complexes a e he only ones ha exhibi an
ex emely s ong saddling2 con ibu ion in
addi ion o saddling1. This s uc u al pa e n
esul s om an an i e omagne ic coupling o he
Cu 3d(x²-y²) elec on wi h he co ole π- adical.
The minimal basis he e o e can no desc ibe hese
complexes.
MinimalBasis o Co oles
dom (B₁)
sad (A₂)
u (B₁)
wa x (B₁)
wa y (A₂)
p o (A₂)
Ex endedBasis o Co oles
dom 2 (B₁)
sad 2 (A₂)
u 2 (B₁)
wa x 2 (B₁)
wa y 2 (A₂)
p o 2 (A₂)
# o s uc u es
haha supe saddling go b
Cu
NOOOOOOOOOOOOO,
YOU MUST OBEY THE
MINIMAL BASIS!!!!!!!
-0.034 Å
-0.121 Å
0.008 Å
-0.023 Å
0.461 Å
0.077 Å
0.045 Å
-0.038 Å
0.090 Å
-0.088 Å
0.796 Å
0.002 Å
p o
wa Y
wa X
u
sad
dom
Doop= 0.910 Å
δoop = 0.001 Å — 0.1 %
Supe saddling!
-0.4
-0.2
0
0.2
0.4
Δmsp/ Å
