TY - JOUR
T1 - Syntheses, structures, two-photon absorption cross-sections and computed second hyperpolarisabilities of quadrupolar A-π-A systems containing E-dimesitylborylethenyl acceptors
AU - Entwistle, Christopher D.
AU - Collings, Jonathan C.
AU - Steffen, Andreas
AU - Pålsson, Lars Olof
AU - Beeby, Andrew
AU - Albesa-Jové, David
AU - Burke, Jacquelyn M.
AU - Batsanov, Andrei S.
AU - Howard, Judith A.K.
AU - Mosely, Jackie A.
AU - Poon, Suk Yue
AU - Wong, Wai Yeung
AU - Ibersiene, Fatima
AU - Fathallah, Sofiane
AU - Boucekkine, Abdou
AU - Halet, Jean Franois
AU - Marder, Todd B.
N1 - Copyright:
Copyright 2011 Elsevier B.V., All rights reserved.
PY - 2009/10/28
Y1 - 2009/10/28
N2 - A series of bis(E-dimesitylborylethenyl)-substituted arenes, namely arene = 1,4-benzene, 1,4-tetrafluorobenzene, 2,5-thiophene, 1,4-naphthalene, 9,10-anthracene, 4,4′-biphenyl, 2,7-fluorene, 4,4′-E-stilbene, 4,4′-tolan, 5,5′-(2,2′-bithiophene), 1,4-bis(4-phenylethynyl) benzene, 1,4-bis(4-phenylethynyl)tetrafluorobenzene and 5,5″-(2,2′: 5′,2″-terthiophene), have been synthesised via hydroboration of the corresponding diethynylarenes with dimesitylborane. Their absorption and emission maxima, fluorescence lifetimes and quantum yields are reported along with the two-photon absorption (TPA) spectra and TPA cross-sections for the 5,5′-bis(E-dimesitylborylethenyl)-2,2′-bithiophene and 5,5′-bis(E-dimesitylborylethenyl)-2,2′:5′,2″- terthiophene derivatives. The TPA cross-section of the latter compound of ca. 1800 GM is the largest yet reported for a 3-coordinate boron compound and is in the range of the largest values measured for quadrupolar compounds with similar conjugation lengths. The X-ray crystal structures of 1,4-benzene, 2,5-thiophene, 4,4′-biphenyl and 5,5″-(2,2′:5′,2″-terthiophene) derivatives indicate π-conjugation along the BCC-arene-CCB chain. Theoretical studies show that the second molecular hyperpolarisabilities, γ, in each series of compounds are generally related to the HOMO energy, which itself increases with increasing donor strength of the spacer. A strong enhancement of γ is predicted as the number of thiophene rings in the spacer increases.
AB - A series of bis(E-dimesitylborylethenyl)-substituted arenes, namely arene = 1,4-benzene, 1,4-tetrafluorobenzene, 2,5-thiophene, 1,4-naphthalene, 9,10-anthracene, 4,4′-biphenyl, 2,7-fluorene, 4,4′-E-stilbene, 4,4′-tolan, 5,5′-(2,2′-bithiophene), 1,4-bis(4-phenylethynyl) benzene, 1,4-bis(4-phenylethynyl)tetrafluorobenzene and 5,5″-(2,2′: 5′,2″-terthiophene), have been synthesised via hydroboration of the corresponding diethynylarenes with dimesitylborane. Their absorption and emission maxima, fluorescence lifetimes and quantum yields are reported along with the two-photon absorption (TPA) spectra and TPA cross-sections for the 5,5′-bis(E-dimesitylborylethenyl)-2,2′-bithiophene and 5,5′-bis(E-dimesitylborylethenyl)-2,2′:5′,2″- terthiophene derivatives. The TPA cross-section of the latter compound of ca. 1800 GM is the largest yet reported for a 3-coordinate boron compound and is in the range of the largest values measured for quadrupolar compounds with similar conjugation lengths. The X-ray crystal structures of 1,4-benzene, 2,5-thiophene, 4,4′-biphenyl and 5,5″-(2,2′:5′,2″-terthiophene) derivatives indicate π-conjugation along the BCC-arene-CCB chain. Theoretical studies show that the second molecular hyperpolarisabilities, γ, in each series of compounds are generally related to the HOMO energy, which itself increases with increasing donor strength of the spacer. A strong enhancement of γ is predicted as the number of thiophene rings in the spacer increases.
UR - http://www.scopus.com/inward/record.url?scp=77749240165&partnerID=8YFLogxK
U2 - 10.1039/b905719f
DO - 10.1039/b905719f
M3 - Article
AN - SCOPUS:77749240165
SN - 0959-9428
VL - 19
SP - 7532
EP - 7544
JO - Journal of Materials Chemistry
JF - Journal of Materials Chemistry
IS - 40
ER -