Chain length effect of spiro-ring N-alkylation on photophysical signalling parameters in Fe(iii) selective rhodamine probes

Abstract

Manifestation of photophysical signalling parameters in rhodamine derivatives exhibiting complexation induced spiro-ring opening is crucial for the realization of selective metal ion detection at trace levels. Substitution of various functional groups, such as alkylation to the core architecture, modulates the physico-chemical properties of such molecular probes. Despite a few studies, relationships between the extent of photophysical signal modulations and the chain lengths of n-alkyl substituents are still elusive. In this investigation, a few molecular probes based on the rhodamine B (1–5) and rhodamine 6G (6–10) platform were synthesized by their derivatization with n-alkyl substituents of varying chain lengths at the amino-donor of their spiro-ring end, which exhibited Fe(III)-selective absorption and fluorescence ‘off–on’ signal transduction along with colorization of solution. The Fe(III)-selectivity in these probes remained the same despite their structural distinctions through varied n-alkyl chain lengths of the substituents; however, the quantifiable signalling parameters such as spectroscopic enhancement factors, sensitivity, the kinetics of spiro-ring opening and effectiveness of probe–Fe(III) interactions were analyzed. These parameters were also correlated in terms of the influence of different chain lengths of n-alkyl substituents that efficiently contributed to their inter-componential interactive stereo-electronic environment.