linear

polarizability

acceptor

Angstrom
acetyl, CH3C(0)Austin-Model 1 elemental

aqueous

analysis
hyperpolarizability exchange exchange

with with

Becke3 Becke3

Lee-Yang-Parr's

correlation functional

B3PW91 BLA

Perdew-Wang
1991 correlation functional

bond-lenght

alternation
sodium tetraborate Na2B407 Becke's broad

exchange

with Perdew's correlation functional
butyl macroscopic susceptibility speed

centi of light

(2.998

s"1)

(10"2)

concentration Coulomb

degree centigrade (0

calculated colum

273.15

cc CEE CI

chromatography
cyanoethynylethene configuration

concentrated interaction

CT CV d
charge-transfer cyclic voltammetry

chemical shift doublet

doublet donor

(multiplicity)

r DANE DCOT DCTB

quinoid

character
1 -(4-dimethylaminophenyl)-6-(4-nitrophenyl)hex-3

-ene-1,5 -diyne

decacyanooctatetraene ^ra5-2-[3-(4-ter^-butylphenyl)-2-methylprop-2-enylidene]malononitrile density-functional theory degenerate

four-wave

mixing
2,5-dihydroxybenzoic iV,iV-dimethylanilino

jV,jV-dimethylformamide

extinction coefficient electric

energy,

charge (1.602

10"19 C)

electric field
potential (electrochemistry), (8.854
dielectric constant electron

10"12

m"1)

EA EDG

e.s.u.

affinity

electron-donating
electron localization function electrostatic units

Et eV 0

electronvolt

(1.602

10"19 J)

moment

quantum yield, hexadecapole

functional calculations. of 76, its radical

structures

TIPS-deprotected analog

anion,

and its dianion

determined

electron localization function character of the dimeric CEEs.

(ELF) analysis.

show the

highly conjugated

MeO-SiMe3

(i-Pr)3Si

Scheme i.

Reversibility

deprotection of CEE 62,

and the oxidative

homo-coupling

of 75,

presents the introduction of strong /V,/V-dimethylanilino (DMA) electron donors

into CEEs.

resulting highly

colored

showed
very strong intramolecular

charge-transfer.

(E)-95, (Z)-95,
and 99 indicated that eis donoris

acceptor conjugation is

disfavored. The

effective than trans

conjugation. Cross-conjugation

strongly

and UV/VIS data show
variation in the width of the transitions in the
band gaps within the series of donor-substituted CEEs. UV/VIS spectra reach from A^ax

lowest-energy

(for (Z)-95)

into the near-IR

for The

The band gap

found to be

highly dependent

the substitution pattern.

extended

chromophores,
131, exhibited unexpectedly isolated donor and acceptor parts.

HOMO and

This resulted in small band gaps.

39% and

high-energy

low-energy good

level, providing extremely

99 and 110 showed

fluorescence quantum

yields (up

58%, respectively) in hexane-rich solvent mixtures.

polar solvents,

CEE 110

revealed

fluorescence, that

attributed to

charge-transfer

(TICT)

state.
The solvatochromism in the UV/VIS and fluorescence spectra of the donor-substituted CEEs

also studied.

We concluded that the excited state of these molecules is

ground

The solvatochromism of the
centrosymmetric chromophore

change

quadrupole

by going

the excited state.

The TPA

cross-
section of 109 the literature.

found to be three times

higher

than that of the most

common

standard in

This first cross-section value shows the

high potential

of donor-substituted

CEEs for material

of linear

one-photon absorption

scales

linearly

with the

achieve

light, /,

that of TPA scales with

quadratic dependence optical

be used to

high spatial selectivity,
which is very useful for e.g.

data storage.

2) Relatively low-energy photons

be used to reach

excited states,

resulting

photo-induced damage. absorption

may be very weak in the

Linear

region

occurs

and therefore the

penetration

in material and

biological samples

be much

higher.

Several

applications [32]

take benefit from these

advantages,

two-photon

fluorescence

microscopy

biological samples [33, 34], photodynamic therapy [35],

three-dimensional

optical storage [36], high-intensity

optical limiting,

which targets the

protection

of the eyes that

by blocking

light [37-39].

There is

need for

chromophores

undergo
between 800 and 1000 nm, the which

wavelength region

commonly

used lasers and the

transparent.
Because of the lack of molecules with

absorption coefficient,

the so-called

section 2,

practical applications

seemed unattainable.

Since 1998, several groups

developed

organic compounds
values and tried to establish

structure-property

of the first
relationships [40]. macroscopic
Since the cross-section cr2 is correlated to the

imaginary part

relationship
hyperpolarizability chromophores

has been proven

[41], the guidelines for the development of

explored

direction than those for second- and third-order
Where h is the Planck's constant, vthe

frequency,

the number of

photons,

light,

N the number of

absorbing
molecules per unit volume and

^ the macroscopic

third-

susceptibility.

Marder, and

Brdas studied several

The groups of Perry,

distyrylbenzene

derivatives

[42-46]

(Figure 4,

dissolution of 62 in DMF resulted in

black solution and

subsequent
reagent CuCl resulted in the decomposition of the starting material.
Also, attempts with aniline,

Cu(OAc)2

different and

nitrogen

ligands

2,6-lutidine,

dimethylaniline,

Therefore, it

imidazole

CH2C12 led

instantaneous

decomposition nitrogen

of 75. bases to
decided to carry out the reaction in the absence of any attack

the CEE.

Addition of
MeOH/THF solution of 75 after 30 minutes.
resulted in the formation of maximum

(detected by TLC)

observed after
hour, but complete decomposition occurred within

75 and dimer 76

three hours. In of
CH2C12, the stability of monomer

After 18 hours

stirring

in the presence of

22%> of the pure dimer could be isolated in the

(Scheme 16).

Changing acidifying
the solvent to MeCN effect of the

[162] resulted

product.

electron-withdrawing

evidently large enough

achieve the oxidative

We wanted to
in the absence of nitrogen bases!
the influence of the number of cyano groups, substitution pattern, and the the acceptor

conjugation length

dimer 77

strength (vide infra).

For this purpose,

mixed TEE/CEE

prepared (Scheme 17).

TMS-protected

TEE precursor for 78

prepared vinyl

according

procedures by

Sonogashira coupling

TIPS-acetylene

bromide 37

CEE 75

The TMS group
removed with K2C03 in THF/MeOH to afford free

then reacted with 2.5

of 78 in the presence of

Cu(OAc)2,

in dimer 77 in

of 27 %>

These calculations support the

hypothesis

formed in the and dianion.

spectroelectrochemical

radical anion

Inspection

of the bond
of the most stable C2h structures of the
neutral, monoanionic, Upon reduction, the

and dianionic 80

clearly

indicates the and the

conjugated single

of this dimer. The

multiple

bonds become

bonds shorter.

largest changes

double bond "e" and at the
buta-l,3-diynediyl bridge ("i"-"k") (Table 7).

Relatively

"a" and

changes

the cyano group

(bonds

"d")
This is in agreement with the

occur on

observation that the reduction of itself but

does not

the carbon

bridge (vide supra).

and dianion

Table 6.

Calculated and measured values for 80, its radical anion 80'

singlet,

doublet,

Symmetry,

AElumo-homo

/Imax (Calc.)

/Imax (exp.)

multiplicity

C2h, S C2h,D C2h, S c2v, s C2,T

[kcal/mol]

-68.5 -7.75

2.91 1.92 1.88 1.87 3.24

[nm][a]

648 648

80'"
80a2" 80b2" 80c2"
[a] Measured for 76n", with

1.1 11.6

0, 1, 2 in CH2C12.

Table 7.

structure of

80, 80'

80a2 indicated

A/dianionanion

1.168 1.416 1.416 1.168 1.416 1.424 1.211 1.067 1.383 1.239 1.332

80a2"

1.175 1.408 1.408 1.174 1.453 1.427 1.215 1.065 1.363 1.257 1.317

A'amon-neutral

1.164 1.424 1.424 1.164 1.383 1.419 1.210 1.069 1.410 1.222 1.351
+0.004 -0.008 -0.008 +0.004 +0.033 +0.005 +0.001 -0.002 -0.027 +0.017 -0.019
+0.007 -0.008 -0.008 +0.006 +0.037 +0.003 +0.004 -0.002 -0.020 +0.018 -0.015
plots (Figure 26). bonding

character The LUMO

The delocalization in 80 is also visible in the HOMO-LUMO of 80

displays anti-bonding

the double bonds and

single single

bonds.

lengthening

of the double bonds and

shortening

bonds upon reduction

HOMO of 80'" and

(Table 7).

expected,

the LUMO of neutral 80 is identical with the

80a2".

HOMOs and LUMOs of 80, 80'

structures were

ELF is
electron localization function

[176, 177])

and has

analysis (ELF, high

Table 8,

Figures 27-29).

projection

of the electron

in the rather unstable alcohols 91 and 92
with Mn2 gave ketones 93 and 94.

key step

reaction of 93 with 4a
(triisopropylsilyl)but-3-ynenitrile (46)
the two isomers of 95. dark.

Hnig's base, providing

mixture

The isomers could be

separated by (E)-95
The ratio between the isolated

(Z)-95

5:3, but this result

obtained after of

multiple chromatographic purifications (Z)-95
in hexane/CH2Cl2 mixtures.

Solutions

(E)-95

in hexane

isomerization under the influence of residual
observed ratio calculations in
difficult to rationalize indicated

steric

electronic reasons,

although (E)-95.

Spartan [158]
be 0.32 kcal/mol less stable than

of the two isomers

difficult and

initially

[182] due

to very

NMR and UV/VIS spectra.

Such similar spectra

also observed for eis- and trans-p-
(dimethylamino)cinnamonitrile [183].

Scheme 23.

Synthesis of the (Z) and () isomers of 95. a) p-MthNC<$4C=CLi, THF, -15 C^0 C, 91 (60%) or 92 (80%). b) Mn02, CH2C12 or Et20, 93 (80%) or 94 (84%). c) 46, (i-Pr)2EtN, EtOH, (Z)-95 (30%) and ()-95 (50%).

The two isomers could

unambiguously assigned

within

of 1D-NOE

'H-NMR

experiments.

The two

TIPS-groups

molecule showed separate

NMR spectrum, and could be

selectively

irradiated.

(Z)-95,

both irradiations resulted in

at 7.4 ppm.

NOE transfer to the proton meta to the Me2N group of the

aryl ring

(E)-95,
of the two irradiations resulted in

small NOE effect.

also agrees
with the observation that

solid and

two TIPS groups in eis
normally prevent good packing

solid.

By comparing these compounds with their /-nitrophenyl-substituted

analogs (e.g. 13,

TEEs show
similarities and differences appear.
The UV/VIS spectra of the CEEs and
red-shifted /tmax for the
with the donor and acceptor groups in "eis"

position compared

with these groups in "trans"

These results The

reproduced by

ab initio calculations

the TEEs

[184] and the

(Chapter 4).
shifts of the DMA group of the TEEs and CEEs show similar low-field shifts for

the carbons isomers.

and meta to the Me2N group for the eis isomers

the trans

After irradiation
^raws-substituted TEE with the

an excess

molecules,
and trans follow the CTP rules.

However, (Z)-95 shows

for the "eis" isomer.

[187].

higher Rf

the TLC,

suggesting

larger polarity

These inconsistent
between the TEEs and the CEEs caused the initial
of the isomers to be incorrect.
Geminally Monosubstituted Monocyanotriethynylethenes
The first strategy for the

geminally

donor-substituted CEEs with

Knoevenagel supra).

propargyl cyanide

ketone,

before
of the donor-substituted reaction of

unexpectedly propargyl

problematic.

Sonogashira

/V,/V-dimethyl-4-iodoaniline

97 with

yielded
good yields [188] (Scheme 24).

attempted

bromination with CBr4

and PPh3

CH2C12 resulted in

immediate

decomposition application

this bromination

procedure

is common, its

bromides with
strong electron-donating substituents such
anilino groups has not been

DMA group

facilitates the elimination of the bromide and
subsequent polymerization.

and well

An attempt to prepare 96

by TIPS-deprotection

of 46 with TBAF

97 failed

subsequent Sonogashira cross-coupling
7Y,7Y-dimethyl-4-iodoaniline

(Scheme 24).

Me2N<(

)>I*~

)>=/

)>=-

.'"

^Si(i-Pr)3

Scheme 24. Failed 82%. then
synthetic routes toward 96. a) HC=CCH2OH, [PdCl2(PPh3)2], Cul, (i-Pr)2NH, THF, b) CBr4, PPh3, CH2C12, 0 C, decomposition, c) CuCN, DMF. d) Bu4NF, THF, -20 C,

with Ar at -78

degassing
C, then r.t., [PdCl2(PPh3)2], Cul, (i-Pr)2NH, THF, 0%. e) base,
Parallel to these attempts,

tried to

2-chloroacrylonitriles,

which obtain

might undergo

CEE 99

CEE 100 could be
7Y,7Y-dimethyl-4-ethynylaniline

(Schemes 24, 25).

easily synthesized

Wittig-Horner

of ketone 49 with
diethyl cyanomethylphosphonate

[189] did

[114] (Scheme 25). Deprotonation of
100 with LDA and reaction with I2
result in the desired of the the

with two times the

material. of

Savignac

diethyl

1-cyano-l101

halomethylphosphonates by deprotonation

lithium

diethyl cyanomethylphosphonate halogenation

the with

bis(trimethylsilyl)amide (LHMDS) degraded during

C2CI6, C2Cl4Br2,

I2. The

iodo derivative

workup by losing

halogen,

and the bromo derivative

decomposed slowly

temperature, but the chloro derivative 103

found to be stable.

Scheme 25.
Attempted synthesis of 99. a) (EtO)2P(0)CH2CN (101), -BuLi, THF, -78 C, then 49, 94%. -20 C, 0%. c) p-M&2^C(^AC=Cn, [PdCl2(PPh3)2], Cul, b) LDA, -78 C, then I2, -78 C (i-Pr)2NH, THF.

reactions with

chlorides

[191],

decided to prepare The

104 and 105 and to

cross-couple

them with

7Y,7Y-dimethyl-4-ethynylaniline (Scheme 26).

103 with

deprotonation
diethyl 1-chloro-1-cyanomethylphosphonate

-BuLi, followed by

reaction with ketones 49

38 afforded

chlorides 104

105 in excellent

yields.

subsequent Sonogashira

CEEs 99 and 106. 41%) and

reaction with

gave the

corresponding yields

differentially protected (Z)-106

()-106

isolated in
58%>, respectively. Since the Rf value difference

very small

(0.03)

and traces of

isomerization, each isomer could only be isolated
in the presence of ~15%> of the

other isomer

(determined by

^-NMR).

1D-NOE

^-NMR spectroscopy. By

small band gap is obtained. The DMA-TEE bands of

reaches into the near-IR

nm, 1.20
also visible in this spectrum

(Figure 46).

The above

show that the band gap

i.e. not

(insulating!)

units.

Undisturbed,

communicating,

donors and acceptors in

result in

small HOMO-LUMO gap.

The interaction between donors and
acceptors increases the gap. Recently, Bryce and co-workers [206] also showed this principle

TTF-TCNQ diad

(Figure 47).
Two conformations with different HOMO-LUMO

identified.

In the extended conformation the TTF
and TCNQ units did not calculated. The second
influence each other and conformation showed and exhibited

small gap of 0.29 eV

intramolecular electrostatic

stacking

of the donor and acceptor unit

gap of 0.70 eV.

m/VY--V y
TTF-TCNQ diad 142 of Bryce and co-workers, showing extremely small band gap.
in the extended conformation
3.6.6 Oscillator The oscillator

Dipole

Moment

strength /

defined transitions
be calculated from the UV/VIS

values

fully-allowed transition,/equals

be calculated from the

1 and for forbidden

transitions/<

of/can (Eq. 5).

integral

below the

multiplied by

10-9js(v)dv
The transition transition

moment M can

be calculated from the oscillator indication for

strength (Eq. 6).

two-photon absorption (TPA)

properties,

which scale with M

\M\=\ 3/*g2j/l=4.86*10-:

y 871 mecv
With h the Planck constant,

in cm/s and

the electric

charge,

the electronic mass,

the wavenumber in

The transition

oscillator

strengths

Some /-Amino-
and/?- Dimethylamino--Styryl
Derivatives. Selective Detection of the Molecule Level.

J. J. La

Clair,
J. Am. Chem. Soc. 1997, 779, 7676-7684. State of Concanvalin A at the

Carbohydrate-Bound

P. J. E. 1282.

Single

Verdegem, Simple

M. C. F.

Monnee, J. Lugtenburg, J. Org. Chem. 2001, 66,
and Efficient Introduction

[10,20-13C2]at

[10-CH3,

13-13C2]-10-

Methylretinal:

of Substituents

2-Position

2,3-Unsaturated

Iorga,

Ricard,

Savignac,
J. Chem. Soc, Perkin Trans. 1 2000, 3311-3316.

Carbanionic

Displacement

Phosphorus.

Cyanomethylphosphonate

State Structures.

Cyanomethylenediphosphonate. Synthesis

and Solid-

Kosinski,

Heinemann,

Hampel,

Eur. J

Chem. 2001, 3879-

An Iterative M.

Approach

Cz's-Oligodiacetylenes.

Raghu,

Heterocycl.

Chem. 1999, 36, 707-

Chalcogenopyranones

from Disodium

Chalcogenide

Additions to

1,4-Pentadiyn-

3-ones.

The Role of Enol Ethers

Intermediates.

Hoffner,

Schottelius,

Feichtinger,

J. Am. Chem. Soc. 1998, 720,

376-385.

2,5-Didehydropyridine

Drug Design.

Biradical:

Computational, Kinetic,

Trapping

Studies toward

[194] [195]

R. G. F.

Bergman,
Ace Chem. Res. 1973, 6, 25-31. Reactive

1,4-Dehydroaromatics.

Bohlmann,

Schnowsky,

Inhoffen,

Grau, Chem.

1964, 97, 794-800.
Polyacetylenverbindungen,

Mechanismus

Oxydativen
Dimerisierung von Acetylenverbindungen.

Fomina,

Vazquez,

Tkatchouk,

Fomine,
Tetrahedron 2002, 58, 6741-6747.
The Glaser Reaction Mechanism. A DFT

Study.

Katz, K. D. Singer, J. E. Sohn, C. W. Dirk, L. A. King, H. M. Gordon, J. Am.

1987, 709, 6561-6563.

Greatly

Optical Susceptibilities

PhotochemCAD:

141-142.

Computer-Aided Design

Research

Photochemistry.

[208] [209]

Guilbault, Kubin,

Practical Fluorescence, Marcel A. N.

Dekker,

Fletcher,
J. Lumin. 1982, 27, 455-462.

Fluorescence Quantum

Yields of Some Rhodamine

[210] [211]

http://www.probes.com/handbook/tables/0375.html.

Rettig, Top.

Curr. Chem. 1994, 169, 253-299.

Photoinduced

Charge Separation
via Twisted Intramolecular

Transfer States. The

Suppan,

N. 1997.

Ghoneim, Solvatochromism,

Society

Chemistry,

Cambridge,

J. Photochem. Photobiol. A 1990, 50, 293-330.

Solvatochromie Shifts:

The Influence of the Medium

Energy of Electronic

States.

Condon, Phys.

1928, 32, 858-872.
Nuclear Motion Associated with
Electron Transitions in Diatomic Molecules.

Liptay,

Wortmann, H. Schaffrin, O. Burkhard, W. Reitinger, N. Detzer, Chem.

429-438.

Phys. 1988, 720, Centrosymmetric

Molecule.

Excited State
Moments and Polarizabilities of

and Dimeric Molecules.

Bichromophoric

Lueck,

McHale,

Edwards,

J. Am. Chem. Soc. 1992, 114, 2342-2348.

Symmetry-Breaking

Series of

Solvent Effects

the Electronic Structure and

Triphenylmethane Dyes.

Chem. Rev. 1993, 93, 381-433.

in Solid and

Duxbury,

Photochemistry

Photophysics

Triphenylmethane Dyes

Kober,

Liquid

Media.

2098-2104.

Sullivan,
Meyer, Inorg. Chem. 1984, 23,

Transitions. of

Dependence
Metal-to-Ligand Charge-Transfer

Evidence for Initial of

Electron Localization in MLCT Excited-State s
2,2'-Bipyridine Complexes

Ruthenium(II)

Osmium(II).

Cooley,

Bergquist,

of Exciton

Kelley,
J. Am. Chem. Soc. 1990, 772, 2612-2617. in

Determination

Hopping

Tris(bipyridine)

Complexes by

Picosecond Polarized

Absorption Spectroscopy.

Auweraer,

F. C. De

Verbeek,

Depaemelaere,

M. Van der

Schryver,

A. Vaes, D.

Terrell,

S. De Meutter, Chem.

Phys. 1993, 176,

195-213.

Table 20.

data and structure refinement for 66.

Identification code

Moon 1 _d_01

Empirical

Formula

formula

C14H22N2O2S12

306.52

Temperature

173(2)K

1.5418
Wavelength Crystal system

Monoclinic

Unit cell dimensions

8.572(1) ,

15.155(1) , = 101.12(1) 14.294(2) ,

Volume

1822.1(4) 3

1.117 1.793

mm"1

Absorption F(000)

Approximate crystal

Data collection

0.20x0.10x0.08
Nonius C AD4 diffractometer with monochromator

graphite

orange

for data collection

4.29-59.94
Index ranges Collected reflections
0</*<9,0<<16,-16</<15

2943 2638

Unique

reflections correction

[7?(int)

0.031]

Structure solution Structure refinement
Data / restraints / parameters
(direct methods) (full-matrix least-squares

SHELXL97

2638/0/204

1.033 RI R\

Goodness-of-fit

[7> 2o(7)]

Final R indices for

R indices

0.0347, w7?2 0.0423, w7?2

0.0980 0.1067

(all data)

Extinction coefficient

0.0013(3)

0.267 and -0.265

Largest diff peak and hole

e."3

Table 21. Atomic coordinates

C/(eq) is defined

as one
third of the trace of the
equivalent isotropic displacement parameters (2 orthogonalized U1} tensor.

for 66.

Si(l) Si(2) C(l) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(ll) C(12) C(13) N(14) 0(15) C(16) N(17) 0(18)

939(1)

-5108(1) -2762(2) -1156(2) -455(2) 140(2) 682(4) -195(3) 3082(3) -3459(2) -4082(2) -5971(4) -3630(3) -6689(3) -113(2) 1379(2) 2219(2) -3799(2) -5282(2) -6117(2)
-1277(1) 3137(1) 948(1) 779(1) 133(1) -404(1) -2338(2) -1242(2) -1064(2) 1640(1) 2237(1) 2632(2) 4006(2) 3594(2) 1252(1) 1088(1) 1577(1) 440(1) 623(1) 82(1)
7973(1) 3799(1) 5681(1) 5841(1) 6529(1) 7110(1) 7312(2) 8953(2) 8425(2) 5053(1) 4561(1) 2631(2) 3686(2) 4380(2) 5331(1) 5524(1) 4965(1) 6168(1) 6019(1) 6539(1)

35(1) 35(1) 26(1) 26(1) 28(1) 34(1) 55(1) 60(1) 51(1) 29(1) 33(1) 61(1) 47(1) 50(1) 28(1) 30(1) 42(1) 28(1) 29(1) 37(1)
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Table 24.

Hydrogen

coordinates (x

isotropic displacement parameters (2

103) for 66.

H(5A) H(5B) H(5C) H(6A) H(6B) H(6C) H(7A) H(7B) H(7C) H(10A) H(IOB) H(IOC) H(HA) H(11B) H(11C) H(12A) H(12B) H(12C) H(13A) H(15A) H(16A) H(18A)
--1324 --6744 -5122 -6504 -3204 -4144 -2761 -7462 -7227 -6214 --3382 -7095
-2821 -2317 -2435 -1700 -1346 -662 -1524 -486 --23 186

6592 6380

77(9) 101(12) 98(12) 96(11) 106(13) 93(11) 67(8) 107(13) 90(10) 79(10) 102(12) 105(12) 74(9) 54(7) 95(11) 91(10) 73(8) 95(12) 35(6) 80(10) 28(5) 71(9)

Table 25.

data and structure refinement for

Moon2_d_02

C54H84N2S14

436.80

295(2)K

P2l/n (No. 14)

13.320(4) , 7.766(2) , 28.722(5) ,

101.30(2)

2913.5(13) 3

0.996 1.176

0.20x0.07x0.04
Nonius CAD4 diffractometer with monochromator

3.14-54.97

4101 3630

0.017]

\j/-scan

3630/0/305

1.036 R\ R\

[7> 2o(I)]

0.0493, w7?2

0.1373 0.1661

=0.0794, w7?2

0.00063(19)

0.320 and -0.207
Table 26 Atomic coordinates

(Z Z)-74

C/(eq)

defined

equivalent isotropic displacement parameters (2 third of the trace of the orthogonalized U1} tensor
Si(l) Si(2) C(l) C(2) C(3) C(4) C(5) N(6) C(7) C(8) C(9) C(10) C(ll) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22) C(23) C(24) C(25) C(26) C(27) C(28)
2349(1) -2792(1) -100(2) -275(2) -479(2) 45(2) -183(3) -357(3) 800(3) 1428(3) 2820(3) 1967(4) 3650(4) 3395(3) 3982(4) 3014(5) 1597(4) 2310(6) 795(5) -1230(2) -1852(3) -3127(3) -2245(5) -4055(5) -3943(4) -4437(5) -3707(6) -2187(5) -1240(6) -2914(6)