J. Phys. Chem. B and C, v114, Issues 13

Distinguishing Polymorphs of the Semiconducting Pigment Copper Phthalocyanine by Solid-State NMR and Raman Spectroscopy

Medhat A. Shaibat†, Leah B. Casabianca†, Diana Y. Siberio-Prez§‡, Adam J. Matzger*‡ and Yoshitaka Ishii*†

Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607, and Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109
J. Phys. Chem. B, 2010, 114 (13), pp 4400–4406

Abstract: Cu(II)(phthalocyanine) (CuPc) is broadly utilized as an archetypal molecular semiconductor and is the most widely used blue printing pigment. CuPc crystallizes in six different forms; the chemical and physical properties are substantially modulated by its molecular packing among these polymorphs. Despite the growing importance of this system, spectroscopic identification of different polymorphs for CuPc has posed difficulties. This study presents the first example of spectroscopic distinction of α- and β-forms of CuPc, the most widely used polymorphs, by solid-state NMR (SSNMR) and Raman spectroscopy. 13C high-resolution SSNMR spectra of α- and β-CuPc using very-fast magic angle spinning (VFMAS) at 20 kHz show that hyperfine shifts sensitively reflect polymorphs of CuPc. The experimental results were confirmed by ab initio chemical shift calculations. 13C and 1H SSNMR relaxation times of α- and β-CuPc under VFMAS also showed marked differences, presumably because of the difference in electronic spin correlation times in the two forms. Raman spectroscopy also provided another reliable method of differentiation between the two polymorphs.