Luminescence of lanthanide ions: an optical tool against counterfeiting

• Grant number: 21/06326-1
• Support Opportunities: Regular Research Grants
• Start date: November 01, 2021
• End date: October 31, 2023
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
• Principal Investigator: Fernando Aparecido Sigoli
• Grantee: Fernando Aparecido Sigoli
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• City of the host institution: Campinas

Abstract

Security labels such as barcodes or QR codes have been used as anti-counterfeiting tools in passports, drivers' licenses, banknotes, and medicine packs. For such a proposal, luminescent materials invisible to naked eyes but revealed by near-UV radiation have been applied, mainly those based on lanthanide (Ln3+) complexes such as [Eu(tta)3phen] (tta = 2-tenoyltrifluoroacetonate; fen = 1,10- phenanthroline) due to their bright luminescence, narrow emission bands featuring high color purity, strong absorption within the near-UV spectral region and thermal and chemical stability. Yet, the dissemination of knowledge regarding this measurement ends up making it possible for security agents to be included or circumvented during the counterfeiting process. To overcome this issue, circularly polarized luminescence (CPL) appears as an alternative tool since replicating CPL, without advanced knowledge and methods of chiral chemistry, hinders the process of counterfeiting. CPL arises from chiral ligands excited with UV radiation for instance, while it can be easily detected by using photomultipliers adapted with manual polarizers or even adapted 3D glasses. Therefore, this proposal aims to investigate new chiral molecules and their use as ligands in Ln3+ complexes for application as anti-counterfeiting inks. The proposed chiral ligands are bis-oxazolines pyridines and bis-oxazolines pyrazines which will be combined with ²- diketone ligands known as efficient Ln3+ antennas to synthesize heteroleptic complexes combining large emission quantum yield and CPL. The chiral ligands may be used for UCNP surface modification leading to circularly polarized upconversion naoparticles (CP-UCNP) and also interacting them to lanthanide molecular cluster aggregates (MCA). (AU)

Scientific publications

(18)

(The scientific publications listed on this page originate from the Web of Science or SciELO databases. Their authors have cited FAPESP grant or fellowship project numbers awarded to Principal Investigators or Fellowship Recipients, whether or not they are among the authors. This information is collected automatically and retrieved directly from those bibliometric databases.)

BISPO-JR, AIRTON GERMANO; MAZALI, ITALO ODONE; SIGOLI, FERNANDO APARECIDO. Single-center Ln(III) ratiometric luminescent temperature probes based on singlet -> singlet and singlet -> triplet sensitizations. JOURNAL OF MATERIALS CHEMISTRY C, v. 10, n. 38, p. 8-pg., 2022-08-15. (12/11382-9, 13/22127-2, 21/06326-1, 20/02614-0)

COSTA, AUGUSTO IWASHITA; DA SILVA, RAFAELA M. R.; BOTELHO, LUCKERMAN D. G.; COELHO, SERGIO F. N.; SIGOLI, FERNANDO A.; HONORATO, JOAO; ELLENA, JAVIER; MARTINS, FELIPE T.; GOMES, ANGELO M.; NUNES, WALLACE C.; et al. Intensity and lifetime ratiometric luminescent thermometer based on a Tb(iii) coordination polymer. DALTON TRANSACTIONS, v. 53, n. 9, p. 12-pg., 2024-01-03. (17/15850-0, 21/04876-4, 21/06326-1, 21/08111-2)

DE ANDRADE, STEFANO ANGERAMI; BISPO-JR, AIRTON GERMANO; SIMONI, DEBORAH DE ALENCAR; ELLENA, JAVIER; NETO, JOAO HONORATO DE ARAUJO; MAZALI, ITALO ODONE; SIGOLI, FERNANDO APARECIDO. The role of terminal and bridge ligands in the molecular upconversion of lanthanide(iii) 1D coordination polymers. JOURNAL OF MATERIALS CHEMISTRY C, v. N/A, p. 8-pg., 2024-11-15. (20/02614-0, 21/06326-1, 14/50906-9, 17/15850-0, 21/08111-2)

DE MORAIS, AMANDA JUSTINO; BISPO-JR, AIRTON GERMANO; FERREIRA, FLAVIA DE SOUSA; MAZALI, ITALO ODONE; SIGOLI, FERNANDO APARECIDO. Multi-emission processes of hierarchically structured NaGdF4:Tm:Yb:Tb core@shell nanoparticles. NEW JOURNAL OF CHEMISTRY, v. 47, n. 15, p. 8-pg., 2023-03-20. (20/02614-0, 21/08111-2, 21/06326-1)

BISPO-JR, AIRTON G.; GALICO, DIOGO A.; DIAZ-RODRIGUEZ, ROBERTO M.; OVENS, JEFFREY S.; SIGOLI, FERNANDO A.; MURUGESU, MURALEE. The role of terminal ligands in the slow relaxation of magnetisation and luminescence thermometry of dinuclear Nd-III complexes. INORGANIC CHEMISTRY FRONTIERS, v. 10, n. 13, p. 11-pg., 2023-06-06. (21/08111-2, 12/11382-9, 21/06326-1, 19/23763-6, 21/09755-0)

BISPO-JR, AIRTON G.; OLIVEIRA, NAGYLA A.; DIOGENIS, ISABELA M. S.; SIGOLI, FERNANDO A.. Perspectives and challenges in circularly polarized luminescence of lanthanide(III) complexes: From solution-based systems to solid-state applications. Coordination Chemistry Reviews, v. 523, p. 23-pg., 2024-10-16. (20/02614-0, 21/06326-1, 14/50906-9, 21/08111-2)

FREITAS, DANIEL CARNEIRO; MAZALI, ITALO ODONE; SIGOLI, FERNANDO APARECIDO; FRANCISCHINI, DANIELLE DA SILVA; ARRUDA, MARCO AURELIO ZEZZI. The microwave-assisted synthesis of silica nanoparticles and their applications in a soy plant culture. RSC ADVANCES, v. 13, n. 39, p. 9-pg., 2023-09-08. (19/24445-8, 19/00063-9, 14/50906-9, 14/50867-3, 19/00018-3, 21/06326-1, 18/25207-0, 20/08543-7)

BISPO-JR, AIRTON G.; SARAIVA, LEONARDO F.; CARNEIRO NETO, ALBANO N.; COELHO, SERGIO F. N.; MAZALI, ITALO O.; CARLOS, LUIS D.; SIGOLI, FERNANDO A.. Insights into quantum cutting and downshifting contributions to near-infrared Yb^III luminescence in 1D coordination polymers. JOURNAL OF MATERIALS CHEMISTRY C, v. N/A, p. 9-pg., 2025-10-14. (19/23763-6, 23/05718-9, 14/50906-9, 21/09755-0, 21/06326-1)

DIOGENIS, ISABELA MOREIRA SOARES; BISPO-JR, AIRTON GERMANO; PIROVANI, RODRIGO VEZULA; SARAIVA, LEONARDO FIGUEIREDO; GOZZO, FABIO CESAR; CORREIA, CARLOS ROQUE DUARTE; MAZALI, ITALO ODONE; NOME, RENE ALFONSO; SIGOLI, FERNANDO APARECIDO. Towards opto-structural parameters to enhance the circularly polarized luminescence brightness of Eu^III β-diketone complexes with chiral auxiliary ligands. JOURNAL OF MATERIALS CHEMISTRY C, v. 12, n. 14, p. 11-pg., 2024-03-11. (14/25770-6, 20/02614-0, 21/06326-1, 14/50906-9, 23/00383-9)

BISPO JR, AIRTON G.; SARAIVA, LEONARDO F.; LIMA, SERGIO A. M.; PIRES, ANA M.; MAZALI, I. O.; SIGOLI, FERNANDO A.. Lanthanide coordination polymers as luminescent thermometers: integrating theoretical modeling with experimental analysis to tune the thermal response. JOURNAL OF MATERIALS CHEMISTRY C, v. 13, n. 7, p. 11-pg., 2024-12-16. (23/05718-9, 21/08111-2, 20/02614-0, 14/50906-9, 21/06326-1)

LIMA, DEBORAH A.; BISPO JR, AIRTON G.; GALICO, DIOGO A. .; COELHO, SERGIO F. N.; NETO, JOAO H. ARAUJO; ELLENA, JAVIER A.; PETIOTE, LANOUSSE; MAZALI, ITALO O.; SIGOLI, FERNANDO A. .. Tuning the Thermometric Features in 1D Luminescent EuIII and TbIII Coordination Polymers through Different Bridge Phosphine Oxide Ligands. Inorganic Chemistry, v. 62, n. 17, p. 9-pg., 2023-04-17. (21/04876-4, 20/02614-0, 21/08111-2, 17/08098-0, 21/06326-1)

GALICO, DIOGO ALVES; MAZALI, ITALO ODONE; SIGOLI, FERNANDO APARECIDO. Bifunctional Temperature and Oxygen Dual Probe Based on Anthracene and Europium Complex Luminescence. INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES, v. 23, n. 23, p. 15-pg., 2022-12-01. (13/22127-2, 21/06326-1, 14/50906-9)

CALADO, CLAUDIA M. S.; MANALI, ISIS F.; DIOGENIS, ISABELA M. S.; COELHO, SERGIO F. N.; TEXEIRA, VERONICA C.; DE MESQUITA, BRUNO R.; OLIVEIRA, JOESLEI L.; SIGOLI, FERNANDO A.; REZENDE, MARCOS V. DOS S.. Defect disorder and optical spectroscopy study of Eu-doped NaYF4 and NaYGdF4 nanoparticles. Optical Materials, v. 137, p. 9-pg., 2023-01-31. (14/50906-9, 21/06326-1)

BISPO, AIRTON GERMANO; GALICO, DIOGO ALVES; OVENS, JEFFREY S.; SIGOLI, FERNANDO APARECIDO; MURUGESU, MURALEE. Impacts of β-diketonate terminal ligands on slow magnetic relaxation and luminescence thermometry in dinuclear Dy^III single-molecule magnets. DALTON TRANSACTIONS, v. N/A, p. 12-pg., 2025-01-02. (19/23763-6, 12/11382-9, 21/08111-2, 21/09755-0, 21/06326-1)

BISPO-JR, AIRTON GERMANO; YEH, LAURENCE; ERRULAT, DYLAN; GALICO, DIOGO ALVES; SIGOLI, FERNANDO APARECIDO; MURUGESU, MURALEE. Improving the performance of & beta;-diketonate-based Dy-III single-molecule magnets displaying luminescence thermometry. CHEMICAL COMMUNICATIONS, v. 59, n. 56, p. 4-pg., 2023-06-16. (19/23763-6, 21/09755-0, 21/06326-1, 21/08111-2)

COELHO, SERGIO FERNANDO NUNES; BISPO-JR, AIRTON GERMANO; DE OLIVEIRA, NAGYLA ALVES; MAZALI, ITALO ODONE; SIGOLI, FERNANDO APARECIDO. Eu^III and Tb^III upconversion intermediated by interparticle energy transfer in functionalized NaLnF₄ nanoparticles. NANOSCALE, v. 16, n. 15, p. 11-pg., 2024-03-05. (14/25770-6, 20/02614-0, 21/06326-1, 14/50906-9, 21/08111-2, 23/00383-9)

SARAIVA, LEONARDO F.; BISPO, AIRTON G.; COSTA, ANDRE L.; SIGOLI, FERNANDO A.; LIMA, SERGIO A. M.; PIRES, ANA M.. Dimensionality Reduction Expands the Frontiers of Lanthanide Luminescence Thermometry Beyond Single-Parametric Thermal Sensing. CHEMISTRY OF MATERIALS, v. N/A, p. 12-pg., 2025-04-16. (21/06326-1, 21/08111-2, 23/05718-9)

SOUSA, GESIANE P.; DE BARROS, ANERISE; SHIMIZU, FLAVIO M.; SIGOLI, FERNANDO A.; MAZALI, ITALO O.. Plasmonic Photocatalysis Driven by Indirect Gold Excitation Via Upconversion Nanoparticle Emission Monitored In Situ by Surface- Enhanced Raman Spectroscopy. ACS APPLIED NANO MATERIALS, v. 6, n. 11, p. 13-pg., 2023-04-13. (14/50906-9, 21/06326-1, 22/02893-1)