Confinement of a Styryl Dye into Nanoporous Aluminophosphates: Channels vs. Cavities
Styryl dyes are generally poor fluorescent molecules inherited from their flexible molecular structures. However, their emissive properties can be boosted by restricting their molecular motions. A tight confinement into inorganic molecular sieves is a good strategy to yield highly fluorescent hybrid...
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MDPI AG
2024-03-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/25/7/3577 |
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| author | Ainhoa Oliden-Sánchez Rebeca Sola-Llano Joaquín Pérez-Pariente Luis Gómez-Hortigüela Virginia Martínez-Martínez |
| author_facet | Ainhoa Oliden-Sánchez Rebeca Sola-Llano Joaquín Pérez-Pariente Luis Gómez-Hortigüela Virginia Martínez-Martínez |
| author_sort | Ainhoa Oliden-Sánchez |
| collection | DOAJ |
| description | Styryl dyes are generally poor fluorescent molecules inherited from their flexible molecular structures. However, their emissive properties can be boosted by restricting their molecular motions. A tight confinement into inorganic molecular sieves is a good strategy to yield highly fluorescent hybrid systems. In this work, we compare the confinement effect of two Mg-aluminophosphate zeotypes with distinct pore systems (the AEL framework, a one-dimensional channeled structure with elliptical pores of 6.5 Å × 4.0 Å, and the CHA framework, composed of large cavities of 6.7 Å × 10.0 Å connected by eight-ring narrower windows) for the encapsulation of 4-DASPI styryl dye (trans-4-[4-(Dimethylamino)styryl]-1-methylpyridinium iodide). The resultant hybrid systems display significantly improved photophysical features compared to 4-DASPI in solution as a result of tight confinement in both host inorganic frameworks. Molecular simulations reveal a tighter confinement of 4-DASPI in the elliptical channels of AEL, explaining its excellent photophysical properties. On the other hand, a singular arrangement of 4-DASPI dye is found when confined within the cavity-based CHA framework, where the 4-DASPI molecule spans along two adjacent cavities, with each aromatic ring sitting on these adjacent cavities and the polymethine chain residing within the narrower eight-ring window. However, despite the singularity of this host–guest arrangement, it provides less tight confinement for 4-DASPI than AEL, resulting in a slightly lower quantum yield. |
| first_indexed | 2024-04-24T10:44:55Z |
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| id | doaj.art-cbdae4b9ea284fb2a7e44e7104262f5c |
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| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-04-24T10:44:55Z |
| publishDate | 2024-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-cbdae4b9ea284fb2a7e44e7104262f5c2024-04-12T13:19:08ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672024-03-01257357710.3390/ijms25073577Confinement of a Styryl Dye into Nanoporous Aluminophosphates: Channels vs. CavitiesAinhoa Oliden-Sánchez0Rebeca Sola-Llano1Joaquín Pérez-Pariente2Luis Gómez-Hortigüela3Virginia Martínez-Martínez4Departamento de Química Física, Universidad del País Vasco (UPV/EHU), Apartado 644, 48080 Bilbao, SpainDepartamento de Química Física, Universidad del País Vasco (UPV/EHU), Apartado 644, 48080 Bilbao, SpainInstituto de Catálisis y Petroleoquímica (CSIC), c/Marie Curie 2, Cantoblanco, 28049 Madrid, SpainInstituto de Catálisis y Petroleoquímica (CSIC), c/Marie Curie 2, Cantoblanco, 28049 Madrid, SpainDepartamento de Química Física, Universidad del País Vasco (UPV/EHU), Apartado 644, 48080 Bilbao, SpainStyryl dyes are generally poor fluorescent molecules inherited from their flexible molecular structures. However, their emissive properties can be boosted by restricting their molecular motions. A tight confinement into inorganic molecular sieves is a good strategy to yield highly fluorescent hybrid systems. In this work, we compare the confinement effect of two Mg-aluminophosphate zeotypes with distinct pore systems (the AEL framework, a one-dimensional channeled structure with elliptical pores of 6.5 Å × 4.0 Å, and the CHA framework, composed of large cavities of 6.7 Å × 10.0 Å connected by eight-ring narrower windows) for the encapsulation of 4-DASPI styryl dye (trans-4-[4-(Dimethylamino)styryl]-1-methylpyridinium iodide). The resultant hybrid systems display significantly improved photophysical features compared to 4-DASPI in solution as a result of tight confinement in both host inorganic frameworks. Molecular simulations reveal a tighter confinement of 4-DASPI in the elliptical channels of AEL, explaining its excellent photophysical properties. On the other hand, a singular arrangement of 4-DASPI dye is found when confined within the cavity-based CHA framework, where the 4-DASPI molecule spans along two adjacent cavities, with each aromatic ring sitting on these adjacent cavities and the polymethine chain residing within the narrower eight-ring window. However, despite the singularity of this host–guest arrangement, it provides less tight confinement for 4-DASPI than AEL, resulting in a slightly lower quantum yield.https://www.mdpi.com/1422-0067/25/7/3577styryl dyesaluminophosphatesphotoactive hybrid systemsMgAPOAEL frameworkCHA framework |
| spellingShingle | Ainhoa Oliden-Sánchez Rebeca Sola-Llano Joaquín Pérez-Pariente Luis Gómez-Hortigüela Virginia Martínez-Martínez Confinement of a Styryl Dye into Nanoporous Aluminophosphates: Channels vs. Cavities International Journal of Molecular Sciences styryl dyes aluminophosphates photoactive hybrid systems MgAPO AEL framework CHA framework |
| title | Confinement of a Styryl Dye into Nanoporous Aluminophosphates: Channels vs. Cavities |
| title_full | Confinement of a Styryl Dye into Nanoporous Aluminophosphates: Channels vs. Cavities |
| title_fullStr | Confinement of a Styryl Dye into Nanoporous Aluminophosphates: Channels vs. Cavities |
| title_full_unstemmed | Confinement of a Styryl Dye into Nanoporous Aluminophosphates: Channels vs. Cavities |
| title_short | Confinement of a Styryl Dye into Nanoporous Aluminophosphates: Channels vs. Cavities |
| title_sort | confinement of a styryl dye into nanoporous aluminophosphates channels vs cavities |
| topic | styryl dyes aluminophosphates photoactive hybrid systems MgAPO AEL framework CHA framework |
| url | https://www.mdpi.com/1422-0067/25/7/3577 |
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