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The first chloroaluminoborate, CsAlB3O6Cl, with innovative AlO3Cl tetrahedra and a perfect planar arrangement of [B3O6] groups, was structurally designed and synthesized via chlorination of [AlO4] tetrahedra. Simultaneously, the smooth introduction of the [AlO3Cl] group into borates initiates the development of a chloroaluminoborate and greatly enriches the structural chemistry of aluminoborates.

Graphical abstract: CsAlB3O6Cl: the rational construction of a KBBF-type structure with aligned 2∞[AlB3O6Cl] layers via introducing unprecedented [AlO3Cl] tetrahedra

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