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Catenated compounds based on Group 14 Elements (E = Si, Ge, Sn) due to the presence of σ-conjugation along the chain of E atoms (Figure 1) have useful optical, semiconducting and other properties. The development of effective ways of synthesis of such compounds, investigation of their properties and structure, establishment of “structure – property” relationships may be regarded as main goals of chemistry in this field. In this report the recent results obtained in our scientific group (Figure 2) for catenated Group 14 derivatives are presented.