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Interactions of C‐iso‐butyl‐calix[4]resorcinarene (1) with sodium sulfite and formaldehyde solution gave a new water‐soluble sulfonatomethylated calix[4]resorcinarene (C4RS) 2 in a quantitative yield. Treatment of 2 with NaOH in a mixture of water, acetonitrile, and methanol afforded complex [Na4(C4RS‐4H)(CH3CN)(H2O)6]2⋅CH3OH (3). Reaction of 2 with NaOH aqueous solution, followed by addition of cesium chloride, led to isolation of complex Cs4Na[(C4RS)2‐5H)](H2O)2 (4). Cation exchange of aluminum nitrate hydrate with complex 3 afforded complex {Al3(H2O)5[(C4RS)2‐9H)]}2⋅(C2H5OH)2⋅(H2O)4 (5). The three new coordination complexes 3–5 were characterized by single crystal X‐ray diffraction analysis. Complexes 3 and 4 display a two‐dimensional bilayer structure through bridging of the sulfonate groups by sodium/cesium cations. The aluminum sulfonatomethylated calix[4]resorcinarene sheets in complex 5 are associated in a one‐dimensional bilayer arrangement and further connected by hydrogen bonds to form a two‐dimensional network.

Protonation of [(Me3tacn)MoO3] with one or two equivalents of strong proton acid afforded mono‐protonated complex [(Me3tacn)MoVIO2(OH)](CF3SO3) and bi‐protonated complex [(Me3tacn)MoVIO(OH)2](PF6)2, respectively. Sulfidation with iPr2NCS2Na or CS2 in acetonitrile, followed by in situ protonation of [(Me3tacn)MO3] (M=Mo, W), produced two monomeric complexes [(Me3tacn)MoVIO2S] ⋅ (iPr2NH2) ⋅ (PF6) ⋅ CH2Cl2 and [(Me3tacn)WVIO2S], and two dimeric complexes [(Me3tacn)MoVO(μ‐S)2MoVO(κ2‐S2C=O)] ⋅ CH3CN and [(Me3tacn)MoIVO]2(μ‐O)(μ‐S2) ⋅ 2DMF. The crystal structures of the two protonated molybdenum(VI) complexes and the four oxo‐sulfido molybdenum/tungsten complexes have been determined. Moreover, the complexes have been characterized by infrared, Raman, fluorescence and UV‐vis spectroscopies. (Me3tacn=1,4,7‐trimethyl‐1,4,7‐triazacyclonane).