Reactions of the organotin selenide chloride clusters [(R¹ Sn^IV )₃ Se₄ Cl] (A, R¹ =CMe₂ CH₂ C(O)Me) or [(R¹ Sn^IV )₄ Se₆ ] (B) with [Cu(PPh₃ )_3-x Cl_x ] yield cluster compounds with different inorganic, mixed-valence core structures: [Cu₄ Sn^II Sn^IV₆ Se₁₂ ], [Cu₂ Sn^II₂ Sn^IV₄ Se₈ Cl₂ ], [Cu₂ Sn^II Sn^IV₄ Se₈ ], [Cu₂ Sn^II₂ Sn^IV₂ Se₄ Cl₄ ], and [Cu₂ Sn^IV₂ Se₄ ]. Five of the compounds, namely [(CuPPh₃ )₂ {(R¹ Sn^IV )₂ Se₄ }] (1), [(CuPPh₃ )₂ Sn^II {(R² Sn^IV )₂ Se₄ }₂ ] (2), [(CuPPh₃ )₂ (Sn^II Cl)₂ {(RSn^IV )₂ Se₄ }₂ ] (3) [(CuPPh₃ )₂ (Sn^II Cu₂ ){(R¹ Sn^IV )₂ Se₄ }₃ ] (4), and [Cu(CuPPh₃ )(Sn^II Cu₂ ){(R¹ Sn^IV )₂ Se₄ }₃ ] (5) are structurally closely related. They are based on [(CuPPh₃ )₂ {(RSn^IV )₂ Se₄ }_n ] aggregates comprising [(RSn^IV )₂ Se₄ ] and [CuPPh₃ ] building units, which are linked by further metal atoms. A sixth compound, [(CuPPh₃ )₂ (Sn^II Cl)₂ {(R¹ Sn^IV Cl)Se₂ }₂ ] (6), differs from the others by containing [(RSn^IV Cl)Se₂ ] units instead, which affects the absorption properties. The compounds were analyzed by single-crystal X-ray diffraction, NMR and ¹¹⁹ Sn Mössbauer spectroscopy, DFT calculations as well as optical absorption experiments.

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