Quantum Chemistry Study Of The Structures And Porperties Of Tetraaza Porphyrins, Phthalocyanines, Subphthalocyanines, And Their Analogues

1. Inner Hydrogen Atom Transfer in Benzo-Fused Low Symmetrical Metal Free Tetraazaporphyrin and Phthalocyanine Analogues:Density Functional Theory StudiesDensity functional theory (DFT) calculations were carried out to study the inner hydrogen atom transfer in low symmetrical metal free tetrapyrrole analogues ranging from tetraazaporphyrin H2TAP (A0B0C0D0) to naphthalocyanine H2Nc (A2B2C2D2) via phthalocyanine H2Pc (A1B1C1D1). All the transition paths of sixteen different compounds (A0B0C0D0-A2B2C2D2 and A0B0CmDn, m≤n≤3) are fully optimized at the B3LYP/6-31G(d) level and vibration analyses have been conducted to verify the optimized structures. It is revealed that the number and position of fused benzene rings onto the TAP skeleton have significant effect on the potential energy barrier of the inner hydrogen atom transfer. Introducing fused benzene rings onto the hydrogen-releasing pyrrole rings can increase the transitivity of inner hydrogen atom and thus lower the transfer barrier of this inner hydrogen atom while fusing benzene rings onto the hydrogen-accepting pyrrole rings will increase the hydrogen transfer barrier to this pyrrole ring. The transient cis-isomer interintermediate with hydrogen atoms joined to the two adjacent pyrrole rings with less fused benzene rings is much stable than the others. It is also found that the benzene rings fused directly onto pyrrole rings have more effect on the inner hydrogen atom transfer than the outer benzene rings fused onto the periphery of isoindole rings. The present work, representing the first effort towards systematically understanding the effect of ring enlargement through asymmetrical peripheral fusion of benzene ring(s) onto the TAP skeleton on the inner hydrogen transfer of tetrapyrrole derivatives, will be helpful in clarifying the N-H tautomerization phenomenon and detecting the cis-porphyrin isomer in bio-systems.2. Design, Synthesis, Characterization, and OFET Properties of Amphiphilic Heteroleptic Tris(phthalocyaninato) Europium(Ⅲ) Complexes. The Effect of Crown Ether Hydrophilic SubstituentsSubtriazaporphyrin (SubTAP) and subphthalocyanine (SubPc) are cone-shaped macrocyclic compounds consisting of three pyrrole or isoindole units around a boron atom. As the analogues of tetreazaporphyrin (TAP) and phthalocyanine (Pc) with smallerπ-peripheral conjugated system, SubTAP and SubPc have received considerable attention in recent years due to their potential applications as chromophores in nonlinear optical materials, organic lighting emitting displays (OLEDs), photovoltaic devices, tagged molecule for biochemical system, and multicomponent donor-acceptor systems associated with their distinct structural, optical, and electronic properties. In addition, subphthalocyanines have been employed as good starting material for synthesizing asymmetric substituted phthalocyanine compounds.Density functional theory (DFT) and time dependent density functional theory (TDDFT) methods have proved suitable for calculating the energy-minimized structure, electronic distribution, molecular orbitals, infrared (IR) spectrum, electronic transfer, and electronic absorption spectra of a series of porphyrin and phthalocyanine derivatives. This seems also true for the subtriazaporphyrin and subphthalocyanine analogues. Recently, Kobayashi and co-workers investigated the molecular orbitals of symmetrical subtriazaporphyrin (SubTAP, A0B0C0), subphthalocyanine (SubPc, A1B1C1), and subnaphthalocyanine (SubNc, A2B2C2) with the semi-empirical Pariser-Parr-Pople method1. A few years later, comparative calculations on the structure of subphthalocyanine (SubPc, A1B1C1) with different levels including HF/STO-3G, HF/3-21G, HF/6-31G, B3LYP/STO-3G, B3LYP/3-21G, B3LYP/6-31G, and B3LYP/6-31G(d) revealed that B3LYP/6-31G(d) was the most suitable method for calculation of subphthalocyanine systems. The frontier molecular orbitals of subphthalocyanine (SubPc, A1B1C1) were also discussed at the level of B3LYP/6-31G(d). The nonliner optical properties of subphthalocyanine (SubPc, A1B1C1) were calculated at the B3LYP/6-31G(d) level using the ZINDO/S-CIS method. The aromaticity and electrophilicity index of subphthalocyanine (SubPc, A1B1C1) were calculated at the B3LYP/6-31G+(d)//B3LYP/6-31G(d) level. Moreover, the frontier orbitals of subtriazaporphyrin (SubTAP, A0B0C0) were also calculated at the B3LYP/6-31G(d) and B3LYP/6-31G(d,p) levels, revealing the similar results for the molecular orbital calculations. However, it appears that there still exists no theoretical work at the DFT level to systematically study the structure, electronic distribution, molecular orbitals, infrared (IR) spectra, and electronic absorption spectra of a full series of SubTAP and SubPc derivatives especially their benzo-fused low symmetrical analogues.In this paper, we describe the structures and properties of fluoroboron-subtriazaporphyrin (SubTAP) and their benzo-fused low symmetric analogues AaBbCc(3≥a,b,c≥0) investigated on the basis of density functional theory (DFT) and time-dependant density functional theory (TDDFT) calculations. The effect of fused-benzene ring(s) on the structures and properties was also revealed.