High-efficiency long-wavelength NIR iridium complexes constructed by extending rigid coordination and optimizing peripheral donor position to break cocoon into butterfly

•Two NIR-emitting Ir(III) complexes with rigid coordinated cocoon and peripheral TPA are synthesized.•The effect of rigid coordinated cocoon and peripheral TPA position on properties of Ir(III) complexes are studied.•(PyQl-TPA)2Ir(acac) with extending coordinated cocoon behaves stronger SOC, smaller ΔEST and lower reorganized energy.•(PyQl-TPA)2Ir(acac)-doped devices exhibit a NIR emission at 784 nm with a record EQE of 5.42% by solution process.