TY - JOUR

T1 - Fluorinated metal phthalocyanines: from the structure of single crystals and thin films to electronic applications

AU - Klyamer, Darya D.

AU - Bonegardt, Dmitry V.

AU - Sukhikh, Aleksandr S.

AU - Basova, Tamara V.

N1 - The work was supported by the Ministry of Science and Higher Education of Russian Federation.

PY - 2026/10/15

Y1 - 2026/10/15

N2 - Fluoro-substituted metal phthalocyanines (MPcFx), in which fluorine atoms are directly attached to the phthalocyanine macrocycle, represent a distinctive class of functional materials with unique electronic, optical, and structural properties. Despite their early synthesis, renewed interest in MPcFₓ has emerged over the past decade due to exceptional thermal and oxidative stability, tunable energy levels, and versatile semiconducting behavior ranging from unipolar (n- or p-type) to ambipolar, depending on the degree of fluorination. These attributes, combined with their ability to sublimate intact under vacuum, make them ideal candidates for physical vapor deposition (PVD) in thin-film electronic applications. While recent reviews have addressed fluorinated porphyrinoids and phthalocyanines with peripheral fluorinated groups, comprehensive coverage of MPcFx with ring-bound fluorine substituents remains scarce. This review fills that gap by combining advances from the last 10–15 years, focusing on the crystal and thin-film structures of MPcFx, spectral characteristics, and volatility. The morphology, phase composition, and growth dynamics of thin films under varying deposition conditions, such as substrate temperature, surface chemistry, and post-deposition annealing are also discussed. Special attention is given to the relationship between molecular structure, thin-film morphology, and device performance in a wide range of electronic devices, including photovoltaic cells, field-effect transistors, diodes, non-volatile memory elements, spin valves, battery electrodes, and highly sensitive chemical sensors. This review provides a cohesive framework for the future development of high-performance fluorinated phthalocyanine materials by correlating molecular design, solid-state organization, and device functionality.

AB - Fluoro-substituted metal phthalocyanines (MPcFx), in which fluorine atoms are directly attached to the phthalocyanine macrocycle, represent a distinctive class of functional materials with unique electronic, optical, and structural properties. Despite their early synthesis, renewed interest in MPcFₓ has emerged over the past decade due to exceptional thermal and oxidative stability, tunable energy levels, and versatile semiconducting behavior ranging from unipolar (n- or p-type) to ambipolar, depending on the degree of fluorination. These attributes, combined with their ability to sublimate intact under vacuum, make them ideal candidates for physical vapor deposition (PVD) in thin-film electronic applications. While recent reviews have addressed fluorinated porphyrinoids and phthalocyanines with peripheral fluorinated groups, comprehensive coverage of MPcFx with ring-bound fluorine substituents remains scarce. This review fills that gap by combining advances from the last 10–15 years, focusing on the crystal and thin-film structures of MPcFx, spectral characteristics, and volatility. The morphology, phase composition, and growth dynamics of thin films under varying deposition conditions, such as substrate temperature, surface chemistry, and post-deposition annealing are also discussed. Special attention is given to the relationship between molecular structure, thin-film morphology, and device performance in a wide range of electronic devices, including photovoltaic cells, field-effect transistors, diodes, non-volatile memory elements, spin valves, battery electrodes, and highly sensitive chemical sensors. This review provides a cohesive framework for the future development of high-performance fluorinated phthalocyanine materials by correlating molecular design, solid-state organization, and device functionality.

KW - Crystal structure

KW - Fluorinated phthalocyanines

KW - Structure-property correlations

KW - Thin films

UR - https://www.scopus.com/pages/publications/105039855019

UR - https://www.mendeley.com/catalogue/b2d12df4-f3bc-3d0b-9ebe-f2187f25a184/

U2 - 10.1016/j.ccr.2026.218118

DO - 10.1016/j.ccr.2026.218118

M3 - Article

VL - 565

JO - Coordination Chemistry Reviews

JF - Coordination Chemistry Reviews

SN - 0010-8545

M1 - 218118

ER -