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•To clarify the deuteration effect and polymorphism effect on the ff emission of lanthanide complexes, we used phenanthroline and its deuterated one (abbreviated to phen and phen-d8, respectively). Eu, Tb, Gd and Tm ion were used as center metals..•Phen complexes with lanthanide ion form polymorphism such as modification IIa and I. The component ratios of polymorphism of Eu or Tb complexes were estimated...