The present disclosure is directed to novel germanosilicate compositions and methods of producing the same. In particular, this disclosure describes an array of transformations originating from the extra-large-pore crystalline germanosilicate compositions, designated CIT-13, possessing 10- and 14-membered rings. Included among the new materials are the new phyllosilicate compositions, designated CIT-13P, new crystalline microporous germanosilicates including high silica versions of CIT-5 and CIT-13, with and without added metal oxides, and new germanosilicate compounds designated CIT-14 and CIT-15. The disclosure also describes methods of preparing these new germanosilicate compositions as well as the compositions themselves.