Structural characterisation and DFT calculations of three new complexes of zinc phthalocyanine with n-alkylamines

Solvent impact on the planarity and aromaticity of free and monohydrated zinc phthalocyanine: a theoretical study

“…The ionic radius of Zn is 0.88 Å [25], thus the Zn ion is tightly located in the middle of four nitrogen atoms and the observed average Zn-N distance is 1.980 Å [20]. Interestingly, in different studies on five coordinated zinc in n-hexylamine solvate of ZnPc, a significant displacement (by 0.48 Å) of metal ion from the molecular plane was observed by X-ray [26]. Besides, the Zn-N bonds were markedly longer (2.06 Å).…”

“…As for ZnPc, the presence of diffuse functions in basis sets decreases the nonplanarity of the phthalocyanine macrocycle. It is worth mentioning that the recent X-ray studies [26] on three axial ZnPc•••n-alkylamines nicely agree with our data and prove the existence of similar nonplanar structures with d parameter of about 0.5 Å. In addition, the subsequent B3LYP/6-31+G(d) [70] b HF, B3LYP, and MP2 with 6-31G* result from [41] c UB3LYP/6-31G(d,p) data for ZnPc, from [71] d B3LYP/6-31G** data from [34] e B3LYP/6-31G* data for ZnPc, from [72] f X-ray data for ZnPc, from [20] g ED data from [21] h Reinvestigation of ED data from [22] i ED data for SnPc, from [22] j ED data for MgPc, from [22] k Laser-desorption supersonic jet spectroscopy data for H2Pc with D 2h symmetry; planar are also MgPc and ZnPc with D 4h symmetry, from [27] l ED data from [35] [75] e X-ray data for ZnPc•••n-hexylamine, from [24] calculations by these authors [26] closely reproduced the observed crystal structure of these solvates (d was about 0.43 Å …”

From Ethanolamine Precursor Towards ZnO—How N Is Released from the Experimental and Theoretical Points of View

“…First, comparison of the plots involving the Zn(II) and the two heteroatoms of the deprotonated EA (Figure 3) shows that there is not significant variation in the mean Zn–O1 bond length in the whole range of temperatures and this bond undergoes smaller oscillations (≈0.1 Å) than the Zn–N bond (≈0.4 Å). Moreover, in the three temperatures, the Zn–N bond distance clearly exceeds those reported for mononuclear Zn(II) complexes with H 2 N{CH 2 ) n CH 3 } units bound to the Zn(II) atom [46,47]. In view of this, we postulate that during the first steps of the degradation process (which, according to IR studies, occurs between 570 and 670 K), the five-membered chelate ring “Zn(OCH 2 CH 2 NH 2 )” opens up and the binding mode of the deprotonated EA changes from (κ 2 -N,O) – to (κ 1 -O) – .…”

Amine-assisted solubilization of unsubstituted zinc phthalocyanine for film deposition purposes

“…The dual mode of the ZnPc-TEA interaction indicates the successive formation of two axial 1 : 1 and 1 : 2 complexes, thus being in agreement with the thermogravimetric data on solid ZnPc-amine crystals. 14 To rationalize the Soret band splitting, the orbital energy diagram for ZnPc is to be considered. According to the quantum chemical study, 28 the B2 envelope consists of three rather than two p-p* peaks, but one of them is rather weak (to be exact, 8% of the whole B2 envelope) because of meager population of the binding 5a 2u orbital localized on the peripheral benzene rings (see Table 3 in ref.…”