1 Supplementary Information LMCT Facilitated Room Temperature Phosphorescence and Energy Transfer in Substituted Thiophenolates of Gd and Yb Vasily A. Ilichev, a Anton V. Rozhkov, a Roman V. Rumyantcev, a Georgy K. Fukin, a Ivan D. Grishin, b Artem V. Dmitriev, c Dmitry A. Lypenko, c Eugeny I. Maltsev, c Artem N. Yablonskiy, d Boris A. Andreev b,d and Mikhail N. Bochkarev a,b a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina st. 49, 603950 Nizhny Novgorod, Russian Federation b Nizhny Novgorod State University, Gagarina avenue 23/2, 603950 Nizhny Novgorod, Russian Federation c A. N. Frumkin Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences, Leninsky prospect 31, 199071 Moscow, Russian Federation d Institute for Physics of Microstructures of Russian Academy of Sciences, 7 ul. Akademicheskaya, 603950 Nizhny Novgorod, Russian Federation Supporting Information Contents Synthesis of compounds 1-4 1 X-ray extended information 2 PL, PLE and absorbtion spectra of thiophenols SSN(H) and OSN(H) 5 MALDI-TOF spectra of 1-4 complexes 5 Proposed energy transfer scheme 7 V-J-L characteristics of OLEDs 8 Synthesis of compounds 1-4 Synthesis of Gd 2 (OSN) 6 (1) A mixture of 2-(2´-mercaptophenyl)benzoxazole (OSN(H)) (150 mg, 0.66 mmol) and Gd[N(SiMe 3 ) 2 ] 3 (140 mg, 0.22 mmol) in DME (10 ml) was stirred at room temperature for 2 hours. Then solvent and volatile products were removed. The remaining residue was washed with hexane and recrystallized from DME. To eliminate residual DME precipitated yellow crystals were dried for 3 hours at 100 0 C in vacuum to give 1 as yellow powder (128 mg, 70%). Elemental analysis: found C, 56.00; H, 2.85; N, 5.05; S, 11.54; Gd, 18.82 for C 39 H 24 N 3 O 3 S 3 Gd: C, 56.03; H, 2.89; N, 5.03; S, 11.50; Gd, 18.80.IR (Nujol, cm −1 ): 1607 (w), 1588 (m), 1536 (m), 1243 (s), 1196 (w), 1044 (m), 1034 (s), 1003 (w), 815 (s), 759 (m), 745 (s). Synthesis of Gd(SSN) 3 (2) Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is © The Royal Society of Chemistry 2017