Abstract
The Knudsen effusion method with mass spectrometric control of the vapor composition was used to study the possibility of a congruent transition to the gas phase and to estimate the enthalpy of sublimation of metal-free tetrakis(1,2,5-thiadiazolo)porphyrazine and its nickel complex (H2TTDPz and NiTTDPz, respectively). The geometrical and electronic structure of H2TTDPz and NiTTDPz in ground and low-lying excited electronic states were determined by DFT calculations. The electronic structure of NiTTDPz was studied by the complete active space (CASSCF) method, following accounting dynamic correlation by multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2). A geometrical structure of D2h and D4h symmetry was obtained for H2TTDPz and NiTTDPz, respectively. According to data obtained by the MCQDPT2 method, the nickel complex possesses the ground state 1A1g, and the wave function of the ground state has the form of a single determinant. Electronic absorption and vibrational (IR and resonance Raman) spectra of H2TTDPz and NiTTDPz were studied experimentally and simulated theoretically.
Highlights
There is a growing interest in organic materials for application in optoelectronics due to their low-cost, high-throughput film manufacturing by solution-processing techniques, high-flex-stability, easy scaling up and integration in devices [1,2,3]
Substitution of benzene rings in phthalocyanines by aromatic heterocycles, e.g., by pyrazine [12,13] or 1,2,5-chalcogenadiazole [14], have a strong impact on the electronic properties of the central porphyrazine (Pz) core which is common to these systems
We have studied theoretically the structure of MTTDPz complexes with some transition metals [23,27] and in this work we begin an experimental study of these substances
Summary
There is a growing interest in organic materials for application in optoelectronics due to their low-cost, high-throughput film manufacturing by solution-processing techniques, high-flex-stability, easy scaling up and integration in devices [1,2,3]. Compounds based on tetrapyrrole macrocycles have interesting spectral and non-linear optical properties [4] which are practically useful for optical communication, information storage, optical switching and processing of electro-optical signals [5,6,7,8,9,10]. The unsubstituted porphyrazine (or tetra-azaporphyrin) and its metallic derivatives, including the Mg(II), Ni(II) and Cu(II) complexes (MPz), were synthesized in 1952 [11]. Their tetrabenzo fused derivatives, known as phthalocyanines are so far most widely studied. Substitution of benzene rings in phthalocyanines by aromatic heterocycles, e.g., by pyrazine [12,13] or 1,2,5-chalcogenadiazole [14], have a strong impact on the electronic properties of the central porphyrazine (Pz) core which is common to these systems
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