PNNL

Abstract

Despite being an important closo-borate in the condensed phase boron chemistry, isolated B10H102- is electronically unstable and has never been detected in the gas phase. Herein, we report a successful capture of this fleeting species through binding with an octamethylcalix[4]pyrrole (omC4P) molecule to form a stable gaseous omC4P·[B10H10]2- complex and its characterizations utilizing negative ion photoelectron spectroscopy (NIPES). The recorded NIPE spectrum, contributed from both omC4P and [B10H10]2-, is deconvoluted by subtracting the omC4P contribution to yield a [B10H10]2- spectrum. The obtained [B10H10]2- spectrum consists of four major bands spanning electron binding energy (EBE) range from 1 to 5 eV with the EBE gaps matching excellently with the energy intervals of computed highly lying occupied molecular orbitals of the B10H102- dianion. This study showcases a generic method to utilize omC4P to capture unstable multiply charged anions in the gas phase for experimental determination of their electronic structures.