The Roles of Molecular Structure and Effective Optical Symmetry in Evolving Dipolar Chromophoric Building Blocks to Potent Octopolar Nonlinear Optical Chromophores
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- 作者：Tomoya Ishizuka ; Louise E. Sinks ; Kai Song ; Sheng-Ting Hung ; Animesh Nayak ; Koen Clays ; Michael J. Therien
- 刊名：Journal of the American Chemical Society
- 出版年：2011
- 出版时间：March 9, 2011
- 年：2011
- 卷：133
- 期：9
- 页码：2884-2896
- 全文大小：1162K
- 年卷期：v.133,no.9(March 9, 2011)
- ISSN：1520-5126
文摘
A series of mono-, bis-, tris-, and tetrakis(porphinato)zinc(II) (PZn)-elaborated ruthenium(II) bis(terpyridine) (Ru) complexes have been synthesized in which an ethyne unit connects the macrocycle meso carbon atom to terpyridyl (tpy) 4-, 4鈥?, and 4鈥测€?positions. These supermolecular chromophores, based on the ruthenium(II) [5-(4鈥?ethynyl-(2,2鈥?6鈥?2鈥测€?terpyridinyl))-10,20-bis(2鈥?6鈥?bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2鈥?6鈥?2鈥测€?terpyridine)2+ bis-hexafluorophosphate (RuPZn) archetype, evince strong mixing of the PZn-based oscillator strength with ruthenium terpyridyl charge resonance bands. Potentiometric and linear absorption spectroscopic data indicate that for structures in which multiple PZn moieties are linked via ethynes to a [Ru(tpy)2]2+ core, little electronic coupling is manifest between PZn units, regardless of whether they are located on the same or opposite tpy ligand. Congruent with these experiments, pump鈭抪robe transient absorption studies suggest that the individual RuPZn fragments of these structures exhibit, at best, only modest excited-state electronic interactions that derive from factors other than the dipole鈭抎ipole interactions of these strong oscillators; this approximate independent character of the component RuPZn oscillators enables fabrication of nonlinear optical (NLO) multipoles with extraordinary hyperpolarizabilities.
Dynamic hyperpolarizability (尾位) values and depolarization ratios (蟻) were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at an incident irradiation wavelength (位inc) of 1300 nm. The depolarization ratio data provide an experimental measure of chromophore optical symmetry; appropriate coupling of multiple charge-transfer oscillators produces structures having enormous averaged hyperpolarizabilities (尾HRS values), while evolving the effective chromophore symmetry from purely dipolar (e.g., Ru(tpy)[4-(Zn-porphyrin)ethynyl-tpy](PF6)2, 尾HRS = 1280 脳 10鈭?0 esu, 蟻 = 3.8; Ru(tpy)[4鈥?(Zn-porphyrin)ethynyl-tpy](PF6)2, 尾HRS = 2100 脳 10鈭?0 esu, 蟻 = 3.8) to octopolar (e.g., Ru[4,4鈥测€?bis(Zn-porphyrin)ethynyl-tpy]2(PF6)2, 尾HRS = 1040 脳 10鈭?0 esu, 蟻 = 1.46) via structural motifs that possess intermediate values of the depolarization ratio. The chromophore design roadmap provided herein gives rise to octopolar supermolecules that feature by far the largest off-diagonal octopolar first hyperpolarizability tensor components ever reported, with the effectively octopolar Ru[4,4鈥测€?bis(Zn-porphyrin)ethynyl-tpy]2(PF6)2 possessing a 尾HRS value at 1300 nm more than a factor of 3 larger than that determined for any chromophore having octopolar symmetry examined to date. Because NLO octopoles possess omnidirectional NLO responses while circumventing the electrostatic interactions that drive bulk-phase centrosymmetry for NLO dipoles at high chromophore concentrations, the advent of octopolar NLO chromophores having vastly superior 尾HRS values at technologically important wavelengths will motivate new experimental approaches to achieve acentric order in both bulk-phase and thin film structures.
Dynamic hyperpolarizability (尾位) values and depolarization ratios (蟻) were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at an incident irradiation wavelength (位inc) of 1300 nm. The depolarization ratio data provide an experimental measure of chromophore optical symmetry; appropriate coupling of multiple charge-transfer oscillators produces structures having enormous averaged hyperpolarizabilities (尾HRS values), while evolving the effective chromophore symmetry from purely dipolar (e.g., Ru(tpy)[4-(Zn-porphyrin)ethynyl-tpy](PF6)2, 尾HRS = 1280 脳 10鈭?0 esu, 蟻 = 3.8; Ru(tpy)[4鈥?(Zn-porphyrin)ethynyl-tpy](PF6)2, 尾HRS = 2100 脳 10鈭?0 esu, 蟻 = 3.8) to octopolar (e.g., Ru[4,4鈥测€?bis(Zn-porphyrin)ethynyl-tpy]2(PF6)2, 尾HRS = 1040 脳 10鈭?0 esu, 蟻 = 1.46) via structural motifs that possess intermediate values of the depolarization ratio. The chromophore design roadmap provided herein gives rise to octopolar supermolecules that feature by far the largest off-diagonal octopolar first hyperpolarizability tensor components ever reported, with the effectively octopolar Ru[4,4鈥测€?bis(Zn-porphyrin)ethynyl-tpy]2(PF6)2 possessing a 尾HRS value at 1300 nm more than a factor of 3 larger than that determined for any chromophore having octopolar symmetry examined to date. Because NLO octopoles possess omnidirectional NLO responses while circumventing the electrostatic interactions that drive bulk-phase centrosymmetry for NLO dipoles at high chromophore concentrations, the advent of octopolar NLO chromophores having vastly superior 尾HRS values at technologically important wavelengths will motivate new experimental approaches to achieve acentric order in both bulk-phase and thin film structures.