Volumetric properties of methyl,tert-butyl, and alkoxy derivatives of tetraphenylporphyrin in benzene solution

• Published in: Journal of solution chemistry Vol. 26; no. 7; pp. 663 - 679
• Main Authors: Zielenkiewicz, W., Perlovich, G. L., Nikitina, G. E., Golubchikov, O. A.
• Format: Journal Article
• Language: English
• Published: New York Springer Nature B.V 01.07.1997
• Subjects: Alkanes; Benzene; Crown ethers; Cyclic compounds; Fatty acids; Hydrocarbons; Mathematical analysis; Molar volume; Porphyrins; Thermal expansion; Topology
• ISSN: 0095-9782; 1572-8927
• DOI: 10.1007/BF02767620

Densities, apparent molar volumes, and partial molar volumes of benzene solutions ofmeso-tetradimethylphenyl porphyrin derivatives H2T(i,j-CH3)PP (where i,j = 2,3-; 2,4-; 3,4-; 2,5-; 3,5-);meso-tetra-4-alkoxyphenyl porphyrin derivatives H2T(4-OCnH2n+1)PP (wheren = 2–4,6–8,10,12,16);meso-tetra-3-butoxyphenyl porphyrin H2T(3-OC4H9)PP;meso-tetra-4-tert-butylphenyl porphyrin H2T(4tBu)PP;meso-tetra-3,5-ditert-butylphenyl porphyrin H2T(3,5-tBu)PP at 25°C and tetraphenylporphyrin, H2TPP,H2T(4-OC10H21)PP;H2T(4-OC12H25)PP and H2T(4tBu)PP at 20°C; 30°C; 40°C; 50°C were determined. The solubilities of the compounds in benzene at 25°C were measured. The solvent excluded volumes for different conformational states and the topology of dimethyl derivatives of tetraphenylporphyrin were calculated and compared with partial molar volume data. The correlation between the partial molar volumes and van der Waals volumes for the derivatives H2TPP,n-alkanes,n-alkanols, fatty acids, cyclic compounds, and crown ethers using the equation of Terasawa was elaborated. The average increment of the methylene group for alkoxy-substituted H2TPP was calculated as δV2o(CH2) = 16.6±0.4cm3-mol-1. The volumetric expansion coefficients of benzene solutions of H2TPP; H2T(4-OC10,H21)PP; H2T(4-OC12H25)PP and H2T(4-tBu)PP were determined and discussed. The importance of packing efficiencies around the solute molecules were examined.