S1 Supporting Information For Synthesis of a Black Dye with Absorption Capabilities Across the Visible-to- Near-Infrared Region: A MO-Mixing Approach via Heterometal Coordination of Expanded Porphyrinoid Yue Wang, † Hiroto Kai, † Masatoshi Ishida,* ,† Sabapathi Gokulnath, ‡ Shigeki Mori, § Tomotaka Murayama, ⊥ Atsuya Muranaka, à Masanobu Uchiyama, ⊥,à Yuhsuke Yasutake, ǁ Susumu Fukatsu, ǁ Yusuke Notsuka, ∇ Yoshihisa Yamaoka, ∇ Mamiko Hanafusa, O Michito Yoshizawa,* ,O Gakhyun Kim, ¶ Dongho Kim,* ,¶ and Hiroyuki Furuta* ,† † Department of Chemistry and Biochemistry, Graduate School of Engineering and Center for Molecular Systems, Kyushu University, Fukuoka 819-0395, Japan ‡ Indian Institute of Science Education and Research (IISER), Thiruvananthapuram, Kerala 695581, India § Advanced Research Support Center (ADRES), Ehime University, Matsuyama 790-8577, Japan ⊥ Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan à Elements Chemistry Laboratory, RIKEN and Advanced Elements Chemistry Research Team, RIKEN Center for Emergent Matter Science (CEMS), Saitama 351-0198, Japan ǁ Graduate School of Arts and Sciences, The University of Tokyo, Tokyo 153-8902, Japan ∇ Department of Advanced Technology Fusion, Graduate School of Science and Engineering, Saga University, Saga 840-8502, Japan O Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, Yokohama 226-8503, Japan ¶ Department of Chemistry and Spectroscopy Laboratory for Functional π-Electronic Systems, Yonsei University, Seoul 03722, Korea Contents 1. Experimental details and synthesis of AuPd-1-------------------------------------------------S2–S5 2. Crystallographic data-----------------------------------------------------------------------------------S6 3. NMR spectra of AuPd-1-------------------------------------------------------------------------------S7 4. Optical spectroscopic data------------------------------------------------------------------------------S8 5. Electrochemical properties-----------------------------------------------------------------------------S9 6. MALDI-TOF-Mass spectrum------------------------------------------------------------------------S10 7. Theoretical calculation--------------------------------------------------------------------------S10–S16 8. MCD spectra of compounds--------------------------------------------------------------------------S17 9. Evolution spectra of AuPd-1-------------------------------------------------------------------------S18 10. Molecular structures of NIR dyes in this study-----------------------------------------------------S18 11. Photo-thermal studies---------------------------------------------------------------------------S19–S20 12. Preparation of AuPd-1Ì(8)m -------------------------------------------------------------------S21–S22 13. Photoacoustic studies----------------------------------------------------------------------------------S22 14. Cartesian coordinates----------------------------------------------------------------------------S23–S33 15. References----------------------------------------------------------------------------------------------S34