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A novel rhodamine based 2-guanidinobenzimidazole functionalized probe RhoG was rationally designed and synthesized for the detection of tetravalent tin in environmental, geological, and biological samples with excellent selectivity, sensitivity, photostability and anti-interference performance. The mechanism investigation confirmed that guanidinobenzimidazole provided binding sites for Sn 4+ and facilitate the formation of the complex. Successfully fluorescent imaging experiments in living L929 cells and MG-63 cells by confocal laser scanning microscopy presented a promising candidate for tracking tetravalent tin in biological organisms and processes thus contribute to significant breakthroughs in understanding the critically important functions of tetravalent tin. [ABSTRACT FROM AUTHOR]