title: Methyloxy substituted heteroleptic bis(phthalocyaninato) yttrium complexes: density functional calculations.
abstract: The effects of alkyloxy substituents attached to one phthalocyanine ligand of three heteroleptic bis(phthalocyaninato) yttrium complexes Y(Pc)[Pc(alpha-OCH3)4] (1), Y(Pc)[Pc(alpha-OCH3)8] (2), and Y(Pc)[Pc(beta-OCH3)8] (3), as well as their reduction products {Y(Pc)[Pc(alpha-OCH3)4]}- (4), {Y(Pc)[Pc(alpha-OCH3)8]}- (5), and {Y(Pc)[Pc(beta-OCH3)8]}- (6) [H2Pc(alpha-OCH3)4=1,8,15,22-tetrakis(methyloxy)phthalocyanine; H2Pc(alpha-OCH3)(8)=1,4,8,11,15,18,22,25-octakis(methyloxy)phthalocyanine; H2Pc(beta-OCH3)(8)=2,3,9,10,16,17,23,24-octakis(methyloxy)phthalocyanine] are studied by DFT calculations. Good consistency is found between the calculated results and experimental data for the electronic absorption, IR, and Raman spectra of 1 and 3. Introduction of electron-donating methyloxy groups on one phthalocyanine ring of the heteroleptic double-deckers induces structural deformation in both phthalocyanine ligands, electron transfer between the two phthalocyanine rings, changes in orbital energy and composition, shift of electronic absorption bands, and different vibrational modes of the unsubstituted and substituted phthalocyanine ligands in the IR and Raman spectra in comparison with the unsubstituted homoleptic counterpart Y(Pc)(2). The calculations reveal that incorporation of methyloxy substituents at the nonperipheral positions has greater influence on the structure and spectroscopic properties of bis(phthalocyaninato) yttrium double-deckers than at the peripheral positions, which increases with increasing number of substituents. Nevertheless, the substituent effect of alkyloxy substituents at one phthalocyanine ligand of the double-decker on the unsubstituted phthalocyanine ring and on the whole molecule and the importance of the position and number of alkyloxy substituents are discussed. In addition, the effect of reducing 1-3 to 4-6 on the structure and spectroscopic properties of the bis(phthalocyaninato) yttrium compounds is also discussed. This systemic DFT study is not only useful for understanding the structure and spectroscopic properties of bis(phthalocyaninato) rare earth metal complexes but also helpful in designing and preparing double-deckers with tunable structure and properties.
authors.affiliation: Key Lab for Colloid and Interface Chemistry, Ministry of Education, Department of Chemistry, Shandong University, Jinan, 250100, PR China.
authors.forename: Yuexing
authors.initials: Y
authors.lastname: Zhang
authors.forename: Xue
authors.initials: X
authors.lastname: Cai
authors.forename: Dongdong
authors.initials: D
authors.lastname: Qi
authors.forename: Ping
authors.initials: P
authors.lastname: Yao
authors.forename: Yongzhong
authors.initials: Y
authors.lastname: Bian
authors.forename: Jianzhuang
authors.initials: J
authors.lastname: Jiang