Synthesis,Conductivity and Photosensitivity of 2-D Conjugated Polymers of Metal-porphyrazine with Sulfur Bridges

The title polymers PMS 8Pz,M=Mn Ⅱ,Fe Ⅱ,Co Ⅱ,Ni Ⅱ,Cu Ⅱ,Zn Ⅱ,were synthesized by teaction of 2,3,5,6 tetracyano 1,4 dithiin with corresponding metal salts ,respectively.The styucture and properties of these polyers were characterized by elemental analysis,transmission electron microscope,DTA,IR, UV Vis,fluorescence and EPR spectra. It has been found that these conjugated polymers have the property of intrinsic semiconductor. The conductivity σ 298K of these polymers is in the range of 10 -9 ￣10 -3 S · cm -1 under pressure 10.63 MPa and incremental in the metal orderMn < Co<Fe<Zn<Cu<Ni.\ The photosensitivity of the MS 8Pz to the CdS PVA films is incremental in the metal order Zn < Mn < Co < Fe < Cu < Ni.

Density functional theory study on organic semiconductor for field effect transistors: Symmetrical and unsymmetrical porphyrazine derivatives with annulated 1,2,5-thiadiazole and 1,4-diamyloxybenzene moieties

Density functional theory (DFT) calculations were carried out to investigate the organic field effect transistor (OFET) performance of the symmetrical metal-free tetrakis (1,2,5-thiadiazole) porphyrazine (S4)PzH2 and tetrakis (1,4-diamyloxybenzene) (A4)PzH2 as well as the low-symmetry metal-free porphy- razine with annulated 1,2,5-thiadiazole and 1,4-diamyloxybenzene groups in the ratio 2:2 (cis) and 1:3, that is, (cis-S2A2)PzH2 and (SA3)PzH2, (S = 1,2,5-thiadiazole ring, A = annulated 1,4-diamyloxy-benzene ring, Pz = porphyrazine) in terms of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy, ionization energy (IE), electron affinity (EA), and their reorganization energy (λ) during the charge-transport process. On the basis of Marcus electron transfer theory, electronic couplings (V) and field effect transistor (FET) properties for the four compounds with known crystal structure have been calculated. The electron transfer mobility (μ -) is revealed to be 0.056 cm2·V-1·s-1 for (S4)PzH2. The hole transfer mobility (μ+) is 0.075, 0.098, and 8.20 cm2·V-1·s-1 for (cis-S2A2)PzH2, (SA3)PzH2, and (A4)PzH2, respectively. The present work represents the theoretical effort towards understanding the OFET properties of symmetrical and unsymmetrical porphyrazine derivatives with annulated 1,2,5-thiadiazole and 1,4-diamyloxybenzene.

Structures and properties of metal-free and magnesium tetrathieno[2,3-b]porphyrazine investigated using density functional theory

Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculation were adopted to study the structures and properties of metal-free and magnesium tetrathieno[2,3-b]porphyrazine (TTPPzH2 and TTPPzMg) using B3LYP method with the 6-31G(d) basis set.A comparison of the geometrical structures,atomic charges,molecular orbitals,UV-vis spectra and infrared (IR) spectra among tetrathieno[2,3-b]porphyrazine (TTPPzH2),phthalocyanine (H2Pc) and porphyrazine (H2Pz) compounds was performed.The substituent effect of the thiophene heterocycle for electron-donating on the structures and properties of these compounds has been discussed.Compared with other atoms,the charge distribution of Cβ atoms adjacent to the sulfur atom is significantly influenced by the thiophene heterocycle substituents.The enlargement of the HOMO-LUMO gaps from H2Pc and MgPc to TTPPzH2 and TTPPzMg is at the origin of the observed blue shift of the Q band when moving from H2Pc to TTPPzH2 compounds.Special emphasis has been devoted to the strongest B bands for TTPPzH2 compounds which show red shift due to the large destabilization of the lower lying occupied orbitals compared with the corresponding B bands of H2Pc compounds.With the assistance of animated pictures produced on the basis of the normal coordinates,the significant peaks and vibration modes in the IR spectra of all the compounds were assigned and analyzed.