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Article Dans Une Revue Journal of Physical Chemistry A Année : 2023

Phospha-cyanines in Their Ideal Polymethine State: Synthesis and Structure–Property Relationships

Résumé

We report the synthesis and full characterization of a family of phosphorus-containing polymethine cyanines (phospha-cyanines). The compounds are easily prepared in two steps, starting from readily available phosphanes. The impact of the P-substituents and the counterions on the structural and optical properties is investigated through a joint experimental/theoretical approach. Based on the study of the single-crystal X-ray diffraction structures, all phospha-cyanines present a bond length alternation close to zero, independently of the substituents and counterions, which indicates an ideal polymethine state. All these compounds display the typical cyanine-like UV–vis absorption with an intense and sharp transition with a vibronic shoulder despite possessing a reverse electronic configuration compared to “classical” cyanines. Time-dependent density-functional theory calculations allowed us to fully rationalize the optical properties (absorption/emission wavelengths, luminescence quantum yields). Interestingly, due to the tetrahedral shape of the P atom, the optical properties are independent of the counterion, which is in marked contrast with N-analogues, which enables predictive engineering of the phospha-cyanines regardless of the medium in which they are used.

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Dates et versions

hal-04331049 , version 1 (08-12-2023)

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Alexandre Chemin, Iryna Knysh, Denis Ari, Marie Cordier, Thierry Roisnel, et al.. Phospha-cyanines in Their Ideal Polymethine State: Synthesis and Structure–Property Relationships. Journal of Physical Chemistry A, 2023, 127 (49), pp.10457-10463. ⟨10.1021/acs.jpca.3c07039⟩. ⟨hal-04331049⟩
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