S1 Supporting Information Anti-[2.2](1,4)Phthalocyaninophane: Spectroscopic Evidence for Transannular Interaction in the Excited Singlet States Yoshiaki Asano, Atsuya Muranaka, Akira Fukasawa, Terutaka Hatano, Masanobu Uchiyama, and Nagao Kobayashi 1. Experimetnal details 1.1. Mesuarements. 1 H NMR spectra were recorded on a JEOL GSX-400 (400 MHz) spectrometer. MALDI-TOF mass spectra were recorded with a Voyager STR spectrometer using α-cyano-4-hydroxy cinnamic acid as the matrix. ESI FT-ICR mass spectra were recorded on a Bruker Daltonics APEX III. Electronic absorption spectra were recorded with a JASCO V-570 spectrometer. Magnetic circular dichroism (MCD) spectra were recorded with a JASCO J-725 spectrodichrometer equipped with a JASCO electromagnet which produced magnetic fields of up to 1.09 T with parallel and antiparallel fields. The magnitude of the MCD signal is expressed in terms of molar ellipticity per tesla [θ] M / deg mol -1 dm 3 cm -1 T -1 . Fluorescence spectra were recorded with a Hitachi F-4500 fluorescence spectrometer. Fluorescence quantum yields were obtained using tetra-tert-butylated zinc(II)phthalocyanine (3Zn) ( Φ F = 0.37 in benzene) as a standard. 1 1.2. Syntheses. All commercial chemicals were used as received. 4,5,12,13-Tetrabromo[2.2]paracyclophane was prepared according to the procedure of de Meijere et al. 2 Tetra-tert-butylated phthalocyanine complexes 3 were obtained as byproducts of phthalocyaninophane syntheses. Scheme S1 Br 2 / I 2 CuCN / CuI / Pd(PPh 3 ) 4 / N,N-dimethylethylenediamine diglyme Zn(OAc) 2 / urea quinoline CuCl / urea / (NH 4 ) 6 Mo 7 O 24 4H 2 O CuCl 2 / DBU octan-1-ol 2Zn 1Zn 2Cu 1Cu 7.4 % 2.1 % 18 % 0.7 % 1-chloronaphthalene 51 % Br Br Br Br NC NC CN CN CN CN tBu NC NC CN CN 4,5,12,13-Tetracyano[2.2]paracyclophane Synthesis and characterization of this compound have been reported by Hopf et al. 4 We have synthesized this compound by applying a copper-catalyzed domino halide exchage-cyanation method, as reported by Buchwald et al. 5 Nitrogen gas was bubbled through diethylene glycol dimethyl ether (diglyme, 150 ml) for 30 min, then 4,5,12,13- tetrabromo[2.2]paracyclophane (1.51 g, 2.88 mmol), copper(I) cyanide (1.15 g, 12.8 mmol), copper(I) iodide (0.03 g, 0.16 mmol), tetrakis(triphenylphosphine)palladium(0) (1.99 g, 1.72 mmol), and N,N-dimethylethylenediamine (61 μl,