of this feature was more significant for 4 than for 1, suggestive
of the larger dipole moment.
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Durability of diarylethene derivatives against thermal
decomposition has not been thoroughly investigated. Thus,
the effect of TCNE addition on the thermal durability was also
examined. The open-ring diarylethene 1 showed a 5 wt%
decomposition temperature (Td5%) of 109 1C under nitrogen
flow, whereas that of the closed-ring 2 significantly increased
to 272 1C (Fig. S9 and Table S3, ESIw). The residual soot
amount of 2 at 500 1C was definitely greater than that of 1.
Noticeably, the TCNE-adduct 4 still retained the high thermal
stability with a Td5% of 193 1C, despite the open-ring form of
the diarylethene. Furthermore, the soot amount of 4 at 500 1C
was similar to that of 2, implying the efficient occurrence of
thermally-induced rearrangements of triple bond moieties.
Thermal improvements in terms of cyano-based acceptor
addition are often observed in the case of the postfunctiona-
lization of polymers.12
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TCNE addition reaction by using the isomerisation of the
photochromic diarylethene derivative. The facilitated thermal
ring-opening of the TCNE-adducted diarylethene allowed the
construction of strong acceptor moieties under mild conditions13
and the production of the D–A substituted photochromic
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logic systems will be worthwhile for future work.
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This work was supported by a Grant-in-Aid for Scientific
Research and the Special Coordination Funds for Promoting
Science and Technology from MEXT, Japan and PRESTO, JST.
Notes and references
%
z Crystal data of 1: C31H23F6NS2, T = 123(2) K, triclinic, P1,
a = 11.2172(10) A, b = 14.1305(12) A, c = 18.2407(16) A,
a = 73.8990(10)1, b = 82.837(2)1, g = 77.2150(10)1, V = 2702.8(4) A3,
Z
=
4, rcalcd
= 1.444 g , R1 (I 4 2s(I)) = 0.0520,
cmꢀ3
wR2 (I 4 2s(I)) = 0.1371, CCDC 824641.
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c
This journal is The Royal Society of Chemistry 2011
Chem. Commun., 2011, 47, 9819–9821 9821