Molecular Motion and Environmental Rigidity in the Framework and Ionic Interface Regions of Mesostructured Silica Thin FilmsClick to copy article linkArticle link copied!
Abstract
The rigidochromic probe molecule ClRe(CO)3-2,2‘-bipyridine is used to study the properties of mesostructured silica thin films. The probe serves dual functions: its emission band maximum shifts to higher energy with increasing rigidity of its environment and simultaneously the fluorescence depolarization measures the mobility of the probe molecule itself. Dip-coated, mesostructured 2-d hexagonal thin films doped with ClRe(CO)3-2,2‘-bipyridine are prepared by a one-step, one-pot synthesis procedure using tetraethoxysilane as the silicon source and cetyltrimethylammonium bromide as the structure directing agent. Amorphous silicate films prepared without the surfactant are used as controls. In the freshly prepared mesostructured films, the probe molecules reside in both the silica framework (in a rigid environment) and the ionic interface region near the surfactant headgroups (in a nonrigid environment) as shown by the rigidochromic shift. The fluorescence depolarization confirms the rigidity; the molecule is fixed in position in the silica framework but rotates in the interface region. The spectra of the probe in dried and frozen films show that maximum rigidity is achieved at low temperature.
*
In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 25 publications.
- Fang-Chu Lin, Jeffrey I. Zink. Probing the Local Nanoscale Heating Mechanism of a Magnetic Core in Mesoporous Silica Drug-Delivery Nanoparticles Using Fluorescence Depolarization. Journal of the American Chemical Society 2020, 142
(11)
, 5212-5220. https://doi.org/10.1021/jacs.9b13082
- Clément Sanchez, Cédric Boissière, David Grosso, Christel Laberty and Lionel Nicole. Design, Synthesis, and Properties of Inorganic and Hybrid Thin Films Having Periodically Organized Nanoporosity. Chemistry of Materials 2008, 20
(3)
, 682-737. https://doi.org/10.1021/cm702100t
- Bruce Dunn and Jeffrey I. Zink. Molecules in Glass: Probes, Ordered Assemblies, and Functional Materials. Accounts of Chemical Research 2007, 40
(9)
, 747-755. https://doi.org/10.1021/ar700033b
- Michael H. Huang,, Francisca Kartono,, Bruce Dunn, and, Jeffrey I. Zink, , Guadalupe Valverde and, Jorge García. Hexagonal to Lamellar Mesostructural Changes in Silicate Films Caused by Organic Additives. Chemistry of Materials 2002, 14
(12)
, 5153-5162. https://doi.org/10.1021/cm0207043
- Plinio Innocenzi. Probing the Sol to Gel Transition in the Gel Structure. 2019, 85-95. https://doi.org/10.1007/978-3-030-20030-5_7
- Karen J. Edler. Formation of Ordered Mesoporous Thin Films Through Templating. 2018, 917-983. https://doi.org/10.1007/978-3-319-32101-1_26
- Karen J. Edler. Formation of Ordered Mesoporous Thin Films Through Templating. 2017, 1-67. https://doi.org/10.1007/978-3-319-19454-7_26-1
- Plinio Innocenzi. Probing the Sol-to-Gel Transition in the Gel Structure. 2016, 63-72. https://doi.org/10.1007/978-3-319-39718-4_6
- Donghun Kim, Bradley F. Chmelka. Robust transparent mesoporous silica membranes as matrices for colorimetric sensors. RSC Advances 2015, 5
(21)
, 16549-16553. https://doi.org/10.1039/C4RA10339D
- Youhei Yamamoto, Hiroyuki Takeda, Tatsuto Yui, Yutaro Ueda, Kazuhide Koike, Shinji Inagaki, Osamu Ishitani. Efficient light harvesting via sequential two-step energy accumulation using a Ru–Re5 multinuclear complex incorporated into periodic mesoporous organosilica. Chem. Sci. 2014, 5
(2)
, 639-648. https://doi.org/10.1039/C3SC51959G
- Yaroslav Klichko, Niveen M. Khashab, Ying-Wei Yang, Sarah Angelos, J. Fraser Stoddart, Jeffrey I. Zink. Improving pore exposure in mesoporous silica films for mechanized control of the pores. Microporous and Mesoporous Materials 2010, 132
(3)
, 435-441. https://doi.org/10.1016/j.micromeso.2010.03.024
- A. Paul, M. Sarkar, D.C. Khara, T. Kamijo, A. Yamaguchi, N. Teramae, A. Samanta. Solvation dynamics of a surfactant probe in mesostructured silica-surfactant nanocomposites. Chemical Physics Letters 2009, 469
(1-3)
, 71-75. https://doi.org/10.1016/j.cplett.2008.12.032
- Akira Yamaguchi, Toshio Kamijo, Norio Teramae. Characterization of the Inner Space of Mesostructured Silica by Time-Resolved Fluorescence Spectroscopy. BUNSEKI KAGAKU 2009, 58
(6)
, 507-516. https://doi.org/10.2116/bunsekikagaku.58.507
- Yaroslav Klichko, Monty Liong, Eunshil Choi, Sarah Angelos, Andre E. Nel, J. Fraser Stoddart, Fuyuhiko Tamanoi, Jeffrey I. Zink. Mesostructured Silica for Optical Functionality, Nanomachines, and Drug Delivery. Journal of the American Ceramic Society 2009, 92
(s1)
https://doi.org/10.1111/j.1551-2916.2008.02722.x
- Michael H. Huang, Hermes M. Soyez, Bruce S. Dunn, Jeffrey I. Zink, Allan Sellinger, C. Jeffrey Brinker. In situ fluorescence probing of the chemical and structural changes during formation of hexagonal phase cetyltrimethylammonium bromide and lamellar phase CTAB/Poly(dodecylmethacrylate) sol–gel silica thin films. Journal of Sol-Gel Science and Technology 2008, 47
(3)
, 300-310. https://doi.org/10.1007/s10971-008-1755-7
- Logudurai Radhakrishnan, Akira Yamaguchi, Wensheng Fu, Hideaki Kaneda, Norio Teramae. Integration of mesostructured silica with bathophenanthroline into a porous alumina membrane by one-pot synthesis method. Microporous and Mesoporous Materials 2008, 113
(1-3)
, 139-145. https://doi.org/10.1016/j.micromeso.2007.11.011
- Erik Johansson, Eunshil Choi, Sarah Angelos, Monty Liong, Jeffrey I. Zink. Light-activated functional mesostructured silica. Journal of Sol-Gel Science and Technology 2008, 46
(3)
, 313-322. https://doi.org/10.1007/s10971-007-1661-4
- Purificación Escribano, Beatriz Julián-López, José Planelles-Aragó, Eloisa Cordoncillo, Bruno Viana, Clément Sanchez. Photonic and nanobiophotonic properties of luminescent lanthanide-doped hybrid organic–inorganic materials. J. Mater. Chem. 2008, 18
(1)
, 23-40. https://doi.org/10.1039/B710800A
- S. Angelos, E. Johansson, J. F. Stoddart, J. I. Zink. Mesostructured Silica Supports for Functional Materials and Molecular Machines. Advanced Functional Materials 2007, 17
(14)
, 2261-2271. https://doi.org/10.1002/adfm.200601217
- Mario Pagliaro, Rosaria Ciriminna, Michel Wong Chi Man, Sandro Campestrini. Better Chemistry through Ceramics: The Physical Bases of the Outstanding Chemistry of ORMOSIL. The Journal of Physical Chemistry B 2006, 110
(5)
, 1976-1988. https://doi.org/10.1021/jp055697v
- Altair B. Moreira, Hueder P.M. Oliveira, Teresa D.Z. Atvars, Iara L.T. Dias, Graciliano O. Neto, Elias A.G. Zagatto, Lauro T. Kubota. Direct determination of paracetamol in powdered pharmaceutical samples by fluorescence spectroscopy. Analytica Chimica Acta 2005, 539
(1-2)
, 257-261. https://doi.org/10.1016/j.aca.2005.03.012
- Payam N. Minoofar, Bruce S. Dunn, Jeffrey I. Zink. Multiply Doped Nanostructured Silicate Sol−Gel Thin Films: Spatial Segregation of Dopants, Energy Transfer, and Distance Measurements. Journal of the American Chemical Society 2005, 127
(8)
, 2656-2665. https://doi.org/10.1021/ja045185e
- Lionel Nicole, Cédric Boissière, David Grosso, Alida Quach, Clément Sanchez. Mesostructured hybrid organic–inorganic thin films. Journal of Materials Chemistry 2005, 15
(35-36)
, 3598. https://doi.org/10.1039/b506072a
- Raquel Hernandez, Payam Minoofar, Michael Huang, Anne-Christine Franville, Shinye Chia, Bruce Dunn, Jeffrey I. Zink. Strategies for spatially separating photoactive molecules in mesosfructured sol-gel silicate films. 2003, 413-418. https://doi.org/10.1016/S0167-2991(03)80411-1
- Payam N. Minoofar, Raquel Hernandez, Shinye Chia, Bruce Dunn, Jeffrey I. Zink, Anne-Christine Franville. Placement and Characterization of Pairs of Luminescent Molecules in Spatially Separated Regions of Nanostructured Thin Films. Journal of the American Chemical Society 2002, 124
(48)
, 14388-14396. https://doi.org/10.1021/ja020817n
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.