四-（4-吡啶基）卟啉二酸聚集体的共振拉曼光谱

研究了近激子吸收带激发下四-（4-吡啶基）卟啉二酸（H8TPyP^6＋）聚集体的共振拉曼光谱。测量了H8TPyP^6＋单体和聚集体的紫外可见吸收谱和共振光散射光谱．在氘代位移的基础上结合相关体系振动光谱研究，对测得的H8TPyP^6＋单体和聚集体的拉曼谱带进行了指认．聚集体的形成导致H8TPyP^6＋的卟啉环CC／CN面内伸缩振动向低波数方向位移2-6cm^-1，而卟啉环鞍形面外振动带向高波数方向位移12cm^-1．基于拉曼谱带的强度和频率变化分析了聚集引起的H8TPyP^6＋分了内结构变化和分子间氢键作用．

Resonance Raman Study of Aggregated Meso-tetra(4-pyridinium) porphyrin Diacid

Resonance Raman spectra of aggregated meso-tetra（4-pyridinium）porphyrin diacid （H8TPyP^6＋） were studied with excitation near the exciton absorption bands of 470 nm. The UV-Vis absorption and resonance light scattering spectra of HsTPyP^6＋ monomers and aggregates were also measured. The observed Raman bands of monomeric and aggregated HsTPyP^6＋ were assigned on the basis of the observed deuteration shifts and by comparing with the Raman spectra of analogous porphyrin diacids. Aggregation causes moderate downshifts （2-6 cm^-1） for high-frequency modes involving the in-plane CC/CN stretches of the porphyrin core and a dramatic upshift （12 cm^-1） for the out-of-plane saddling mode of the porphyrin ring. The structural changes induced by aggregation and the possible hydrogen bonding interaction between the HsTPyP^6＋ molecules in the aggregate are discussed based on the spectral observations.