| Title: |
Seeding the vertical growth of laterally coherent coordination polymers on the rutile-TiO2(110) surface |
| Authors: |
Luca Schio; Gregor Bavdek; Cesare Grazioli; Claudia Obersnù; Albano Cossaro; Andrea Goldoni; Alberto Calloni; Alberto Bossi; Gianlorenzo Bussetti; Alessio Orbelli Biroli; Andrea Vittadini; Luca Floreano |
| Contributors: |
Schio, Luca; Bavdek, Gregor; Grazioli, Cesare; Obersnù, Claudia; Cossaro, Albano; Goldoni, Andrea; Calloni, Alberto; Bossi, Alberto; Bussetti, Gianlorenzo; Orbelli Biroli, Alessio; Vittadini, Andrea; Floreano, Luca |
| Publication Year: |
2024 |
| Collection: |
Università degli studi di Trieste: ArTS (Archivio della ricerca di Trieste) |
| Subject Terms: |
Supramolecular assembly; NEXAFS; photoemission |
| Description: |
Coordination polymers may be synthesized by linear bridging ligands to metal ions with conventional chemistry methods (e.g. in solution). Such complexes can be hardly brought onto a substrate with the chemical, spatial and geometrical homogeneity required for device integration. Instead, we follow an in situ synthesis approach, where the anchoring points are provided by a monolayer of metal(II)-tetraphenylporphyrin (M-TPP, M = Cu, Zn, Co) grown in vacuum on the rutile-TiO2(110) surface. We probed the metal affinity to axial coordination by further deposition of symmetric dipyridyl-naphthalenediimide (DPNDI). By NEXAFS linear polarization dichroism, we show that DPNDI stands up on Zn- and Co-TPP thanks to axial coordination, whereas it lies down on the substrate for Cu-TPP. Calculations for a model pyridine ligand predict strong binding to Zn and Co cations, whose interaction with the O anions underneath is disrupted by surface trans effect. The weaker interactions between pyridine and Cu-TPP are then overcome by the strong attraction between TiO2 and DPNDI. The binding sites exposed by the homeotropic alignment of the ditopic DPNDI ligand on Zn- and Co-TPP are the foundations to grow coordination polymers preserving the lateral coherence of the basal layer. |
| Document Type: |
article in journal/newspaper |
| Language: |
English |
| Relation: |
info:eu-repo/semantics/altIdentifier/pmid/38895745; info:eu-repo/semantics/altIdentifier/wos/WOS:001251750000001; volume:16; issue:27; firstpage:13071; lastpage:13078; numberofpages:8; journal:NANOSCALE; https://hdl.handle.net/11368/3080958 |
| DOI: |
10.1039/D4NR01309C |
| Availability: |
https://hdl.handle.net/11368/3080958; https://doi.org/10.1039/D4NR01309C |
| Rights: |
info:eu-repo/semantics/openAccess ; license:Creative commons ; license uri:http://creativecommons.org/licenses/by/4.0/ |
| Accession Number: |
edsbas.33555CB3 |
| Database: |
BASE |