Synthesis, luminescence, and electrochemical studies of tetra- and octanuclear ruthenium(ii) complexes of tolylterpyridine appended calixarenesElectronic supplementary information (ESI) available: Crystallographic data in CIF format, relevant absorption, emission, and excitation spectra of free ligands and complexes, cyclic voltammograms of complexes, mass and NMR spectra of all organic precursors, and free ligands, and mass spectra of complexes. CCDC 720988 (1). For ESI and crystallographic dat

Tetra- and octanuclear Ru( ii ) complexes of tolylterpyridine appended calixarenes, [{Ru(ttpy)} 4 ( L 1 )](PF 6 ) 8 ( 3 ) and [{Ru(ttpy)} 8 ( L 2 )](PF 6 ) 16 ( 4 ) [ L 1 = 5,11,17,23-tetra- tert -butyl-25,26,27,28-tetra(4′- p -benzyloxy-(2,2′:6′,2′′-terpyridinyl))calix[4]arene; L 2 = 5,11,17,23,29,35,41,47-octa- tert -butyl-49,50,51,52,53,54,55,56-octa(4′- p -benzyloxy-(2,2′:6′,2′′-terpyridinyl))calix[8]arene; and ttpy = 4′-( p -tolyl)-2,2′:6′,2′′-terpyridine] have been synthesized and characterized. 5,11,17,23-Tetra- tert -butyl-25,26,27,28-tetrahydroxycalix[4]arene ( 1 ) was characterized using single crystal X-ray diffraction, whereas 5,11,17,23,29,35,41,47-octa- tert -butyl-49,50,51,52,53,54,55,56-octahydroxycalix[8]arene ( 2 ) was characterized using NMR and mass spectrometry. The tetra- and octanuclear complexes 3 and 4 are nonluminescent at 298 K, but exhibit 3 MLCT emission at 650 nm at 77 K in acetonitrile. In the solid state at 298 K they exhibit 3 MLCT emission at 663 and 666 nm, respectively. The polynuclear complexes 3 and 4 containing four and eight [Ru(ttpy) 2 ] 2+ moieties undergo one-electron oxidation at 1.27 and 1.25 V versus Ag/Ag + , respectively, in acetonitrile. This study demonstrates the versatility of the tolylterpyridine appended calix[4]arene and calix[8]arene in forming polynuclear Ru( ii ) complexes. Tetra- and octanuclear ruthenium( ii ) complexes of tolylterpyridine appended calixarenes are synthesized and their luminescence and electrochemical properties are investigated.