Linear and nonlinear optical properties of a macrocyclic trichromophore bundle with parallel-aligned dipole moments.
A macrocyclic trichromophore bundle 1 with parallel-aligned dipole moments has been synthesized to study the influence of aggregation and orientation of a nonlinear optical (NLO) chromophore on its optical properties. The linear and nonlinear optical properties of 1 and a single chromophore standard 2 have been studied by UV-vis absorption, fluorescence, solvatochromic spectrometry, and hyper-Rayleigh scattering (HRS). Reduced first-order hyperpolarizability beta, hypsochromic shift, enhanced solvatochromic shifts, and fluorescence quenching for individual chromophores were observed when 1 was compared with 2. Analysis of the data showed that the transition dipole moment changes only slightly when the chromophores are parallel aligned in the bundle architecture. However, the apparent hyperpolarizability of the individual chromophores decreased significantly by about 20%. The reduction in beta for the individual chromophores in 1 is largely due to the hypsochromic shift, i.e., excitation energy increase of the interband (charge-transfer) energy gap and the reduced difference between the ground-state and excited-state dipole moments. The hypsochromic shift and fluorescence quenching are consistent with exciton theory. Possible reasons for the enhanced solvatochromic shift are discussed.
Liao
Yi
Y
Department of Chemistry, University of Washington, Seattle, Washington 98195, USA. liaoyi@u.washington.edu
Firestone
Kimberly A
KA
Bhattacharjee
Sanchali
S
Luo
Jingdong
J
Haller
Marnie
M
Hau
Steven
S
Anderson
Cyrus A
CA
Lao
David
D
Eichinger
Bruce E
BE
Robinson
Bruce H
BH
Reid
Philip J
PJ
Jen
Alex K-Y
AK
Dalton
Larry R
LR