The low-temperature binding of nitric oxide (NO) in the metal-organic framework MIL-100(Al) has been investigated by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy. Three NO adsorption species have been identified. Among them, one species has been verified experimentally to bind directly to an 27Al atom and all its relevant 14N and 27Al hyperfine interaction parameters have been determined spectroscopically. Those parameters fit well to the calculated ones of a theoretical cluster model, which was derived by density functional theory (DFT) in the present work and describes the low temperature binding of NO to the regular coordinatively unsaturated Al3+ site of the MIL-100(Al) structure. As a result, the Lewis acidity of that site has been characterized using the NO molecule as an electron paramagnetic resonance active probe. The DFT derived wave function analysis revealed a bent end-on coordination of the NO molecule adsorbed at that site which is almost purely ionic and has a weak binding energy. The calculated flat potential energy surface of this species indicates the ability of the NO molecule to freely rotate at intermediate temperatures while it is still binding to the Al3+ site. For the other two NO adsorption species, no structural models could be derived, but one of them is indicated to be adsorbed at the organic part of the metal-organic framework. Hyperfine interactions with protons, weakly coupled to the observed NO adsorption species, have also been measured by pulsed electron paramagnetic resonance and found to be consistent with their attribution to protons of the MIL-100(Al) benzenetricarboxylate ligand molecules.

1.
S.
Kitagawa
and
M.
Kondo
,
Bull. Chem. Soc. Jpn.
71
,
1739
(
1998
).
2.
S.
Kitagawa
,
R.
Kitaura
, and
S.-I.
Noro
,
Angew. Chem., Int. Ed.
43
,
2334
(
2004
).
3.
B.
Li
,
M.
Chrzanowski
,
Y.
Zhang
, and
S.
Ma
,
Coord. Chem. Rev.
307
,
106
(
2016
).
4.
M. I.
Nandasiri
,
S. R.
Jambovane
,
B. P.
McGrail
,
H. T.
Schaef
, and
S. K.
Nune
,
Coord. Chem. Rev.
311
,
38
(
2016
).
5.
R. J.
Kuppler
,
D. J.
Timmons
,
Q.-R.
Fang
,
J.-R.
Li
,
T. A.
Makal
,
M. D.
Young
,
D.
Yuan
,
D.
Zhao
,
W.
Zhuang
, and
H.-C.
Zhou
,
Coord. Chem. Rev.
253
,
3042
(
2009
).
6.
U.
Mueller
,
M.
Schubert
,
F.
Teich
,
H.
Puetter
,
K.
Schierle-Arndt
, and
J.
Pastré
,
J. Mater. Chem.
16
,
626
(
2006
).
7.
J.
Gascon
,
A.
Corma
,
F.
Kapteijn
, and
F. X.
Llabrés i Xamena
,
ACS Catal.
4
,
361
(
2014
).
8.
M.
Haouas
,
C.
Volkringer
,
T.
Loiseau
,
G.
Férey
, and
F.
Taulelle
,
J. Phys. Chem. C
115
,
17934
(
2011
).
9.
L.
Mitchell
,
P.
Williamson
,
B.
Ehrlichova
,
A. E.
Anderson
,
V. R.
Seymour
,
S. E.
Ashbrook
,
N.
Acerbi
,
L. M.
Daniels
,
R. I.
Walton
,
M. L.
Clarke
, and
P. A.
Wright
,
Chem. - Eur. J.
20
,
17185
(
2014
).
10.
M. N.
Timofeeva
,
V. N.
Panchenko
,
A. A.
Abel
,
N. A.
Khan
,
I.
Ahmed
,
A. B.
Ayupov
,
K. P.
Volcho
, and
S. H.
Jhung
,
J. Catal.
311
,
114
(
2014
).
11.
T.
Rudolf
,
W.
Böhlmann
, and
A.
Pöppl
,
J. Magn. Reson.
155
,
45
(
2002
).
12.
V. N.
Panchenko
,
M. M.
Matrosova
,
J.
Jeon
,
J. W.
Jun
,
M. N.
Timofeeva
, and
S. H.
Jhung
,
J. Catal.
316
,
251
(
2014
).
13.
M.
Gaab
,
N.
Trukhan
,
S.
Maurer
,
R.
Gummaraju
, and
U.
Müller
,
Microporous Mesoporous Mater.
157
,
131
(
2012
).
14.
M.
Chiesa
,
E.
Giamello
, and
M.
Che
,
Chem. Rev.
110
,
1320
(
2009
).
15.
A.
Pöppl
,
T.
Rudolf
,
P.
Manikandan
, and
D.
Goldfarb
,
J. Am. Chem. Soc.
122
,
10194
(
2000
).
16.
H.
Brion
,
C.
Moser
, and
M.
Yamazaki
,
J. Chem. Phys.
30
,
673
(
1959
).
17.
G.
Herzberg
and
J. W. T.
Spinks
,
Spectra of Diatomic Molecules
(
D. Van Nostrand Company
,
New York
,
1950
).
18.
E.
Cartmell
and
G. W. A.
Fowles
,
Valency and Molecular Structure
(
Butterworths
,
London
,
1961
).
19.
R. P.
Orenha
and
S. E.
Galembeck
,
J. Chem. Educ.
91
,
1064
(
2014
).
20.
C. L.
Gardner
and
M. A.
Weinberger
,
Can. J. Chem.
48
,
1317
(
1970
).
21.
Z.
Hu
and
D.
Zhao
,
CrystEngComm
19
,
4066
(
2017
).
22.
C.
Volkringer
,
H.
Leclerc
,
J.-C.
Lavalley
,
T.
Loiseau
,
G.
Férey
,
M.
Daturi
, and
A.
Vimont
,
J. Phys. Chem. C
116
,
5710
(
2012
).
23.
H.
Leclerc
,
A.
Vimont
,
J.-C.
Lavalley
,
M.
Daturi
,
A. D.
Wiersum
,
P. L.
Llwellyn
,
P.
Horcajada
,
G.
Ferey
, and
C.
Serre
,
Phys. Chem. Chem. Phys.
13
,
11748
(
2011
).
24.
A.
Vimont
,
J.-M.
Goupil
,
J.-C.
Lavalley
,
M.
Daturi
,
S.
Surble
,
C.
Serre
,
F.
Millange
,
G.
Ferey
, and
N.
Audebrand
,
J. Am. Chem. Soc.
128
,
3218
(
2006
).
25.
B.
Barth
,
M.
Mendt
,
A.
Pöppl
, and
M.
Hartmann
,
Microporous Mesoporous Mater.
216
,
97
(
2015
).
26.
C.
Volkringer
,
D.
Popov
,
T.
Loiseau
,
G.
Férey
,
M.
Burghammer
,
C.
Riekel
,
M.
Haouas
, and
F.
Taulelle
,
Chem. Mater.
21
,
5695
(
2009
).
27.
A.
Aijaz
,
T.
Akita
,
H.
Yang
, and
Q.
Xu
,
Chem. Commun.
50
,
6498
(
2014
).
28.
Y.
Chen
,
B.
Fan
,
N.
Lu
, and
R.
Li
,
Catal. Commun.
64
,
91
(
2015
).
29.
R.
Grall
,
T.
Hidalgo
,
J.
Delic
,
A.
Garcia-Marquez
,
S.
Chevillard
, and
P.
Horcajada
,
J. Mater. Chem. B
3
,
8279
(
2015
).
30.
C.
Janiak
and
J. K.
Vieth
,
New J. Chem.
34
,
2366
(
2010
).
31.
L. J.
Ignarro
and
F.
Murad
,
Nitric Oxide. Biochemistry, Molecular Biology, and Therapeutic Implications
(
Academic Press
,
San Diego
,
1995
).
32.
F. J.
Corpas
and
J. B.
Barroso
,
Nitric Oxide
45
,
15
(
2015
).
34.
G.
Walford
and
J.
Loscalzo
,
J. Thromb. Haemostasis
1
,
2112
(
2003
).
35.
F. C.
Fang
,
J. Clin. Invest.
99
,
2818
(
1997
).
36.
A. R.
Butler
and
D. L. H.
Williams
,
Chem. Soc. Rev.
22
,
233
(
1993
).
37.
J.-D.
Lio
and
A. F.
Chen
,
Acta Pharmacol. Sin.
26
,
259
(
2005
).
38.
P.
Vallance
,
Fundam. Clin. Pharmacol.
17
,
1
(
2003
).
39.
S.
Huerta
,
S.
Chilka
, and
B.
Bonavida
,
Int. J. Oncol.
33
,
909
(
2008
).
40.
J. P.
Maia-de-Oliveira
,
C.
Trzesniak
,
I. R.
Oliveira
,
M. J.
Kempton
,
T. M. N.
de Rezende
,
S.
Iego
,
G. B.
Baker
,
S. M.
Dursun
,
J. P.
Machado-de-Sousa
, and
J. E. C.
Hallak
,
Rev. Bras. Psiquiatr.
34
(
Suppl. 2
),
149
(
2012
).
41.
P. G.
Parzuchowski
,
M. C.
Frost
, and
M. E.
Meyerhoff
,
J. Am. Chem. Soc.
124
,
12182
(
2002
).
42.
F.
DeRosa
,
M. R.
Kibbe
,
S. F.
Najjar
,
M. L.
Citro
,
L. K.
Keefer
, and
J. A.
Hrabie
,
J. Am. Chem. Soc.
129
,
3786
(
2007
).
43.
J. H.
Shin
,
S. K.
Metzger
, and
M. H.
Schoenfisch
,
J. Am. Chem. Soc.
129
,
4612
(
2007
).
44.
J. H.
Shin
and
M. H.
Schoenfisch
,
Chem. Mater.
20
,
239
(
2008
).
45.
D. A.
Riccio
and
M. H.
Schoenfisch
,
Chem. Soc. Rev.
41
,
3731
(
2012
).
46.
P. S.
Wheatley
,
A. R.
Butler
,
M. S.
Crane
,
A. G.
Rossi
,
I. L.
Megson
, and
R. E.
Morris
, in
Molecular Sieves: From Basic Research to Industrial Applications Proceedings of the 3rd International Zeolite Symposium (3rd FEZA)
, Studies in Surface Science and Catalysis, edited by
N. Ž. a. P. N. J.
Čejka
(
Elsevier
,
2005
), pp.
2033
2040
.
47.
P. S.
Wheatley
,
A. R.
Butler
,
M. S.
Crane
,
S.
Fox
,
B.
Xiao
,
A. G.
Rossi
,
I. L.
Megson
, and
R. E.
Morris
,
J. Am. Chem. Soc.
128
,
502
(
2006
).
48.
P. S.
Wheatley
,
A. C.
McKinlay
, and
R. E.
Morris
,
Zeolites and Related Materials: Trends, Targets and Challenges, Proceedings of the 4th International FEZA Conference
(
Elsevier
,
2008
), pp.
441
446
.
49.
M.
Mowbray
,
X.
Tan
,
P. S.
Wheatley
,
R. E.
Morris
, and
R. B.
Weller
,
J. Invest. Dermatol.
128
,
352
(
2007
).
50.
N. J.
Hinks
,
A. C.
McKinlay
,
B.
Xiao
,
P. S.
Wheatley
, and
R. E.
Morris
,
Microporous Mesoporous Mater.
129
,
330
(
2010
).
51.
M. J.
Ingleson
,
R.
Heck
,
J. A.
Gould
, and
M. J.
Rosseinsky
,
Inorg. Chem.
48
,
9986
(
2009
).
52.
K.
Peikert
,
L. J.
McCormick
,
D.
Cattaneo
,
M. J.
Duncan
,
F.
Hoffmann
,
A. H.
Khan
,
M.
Bertmer
,
R. E.
Morris
, and
M.
Fröba
,
Microporous Mesoporous Mater.
216
,
118
(
2015
).
53.
E. D.
Bloch
,
W. L.
Queen
,
S.
Chavan
,
P. S.
Wheatley
,
J. M.
Zadrozny
,
R.
Morris
,
C. M.
Brown
,
C.
Lamberti
,
S.
Bordiga
, and
J. R.
Long
,
J. Am. Chem. Soc.
137
,
3466
(
2015
).
54.
F.
Bonino
,
S.
Chavan
,
J. G.
Vitillo
,
E.
Groppo
,
G.
Agostini
,
C.
Lamberti
,
P. D. C.
Dietzel
,
C.
Prestipino
, and
S.
Bordiga
,
Chem. Mater.
20
,
4957
(
2008
).
55.
J. F.
Eubank
,
P. S.
Wheatley
,
G.
Lebars
,
A. C.
McKinlay
,
H.
Leclerc
,
P.
Horcajada
,
M.
Daturi
,
A.
Vimont
,
R. E.
Morris
, and
C.
Serre
,
APL Mater.
2
,
124112
(
2014
).
56.
A. C.
McKinlay
,
J. F.
Eubank
,
S.
Wuttke
,
B.
Xiao
,
P. S.
Wheatley
,
P.
Bazin
,
J.-C.
Lavalley
,
M.
Daturi
,
A.
Vimont
,
G.
de Weireld
,
P.
Horcajada
,
C.
Serre
, and
R. E.
Morris
,
Chem. Mater.
25
,
1592
(
2013
).
57.
C.
Kim
,
S.
Diring
,
S.
Furukawa
, and
S.
Kitagawa
,
Dalton Trans.
44
,
15324
(
2015
).
58.
T.
Li
,
K.
Taylor-Edinbyrd
, and
R.
Kumar
,
Phys. Chem. Chem. Phys.
17
,
23403
(
2015
).
59.
A.
Schweiger
and
G.
Jeschke
,
Principles of Pulse Electron Paramagnetic Resonance
(
Oxford University Press
,
Oxford, UK, New York
,
2001
).
60.
P.
Höfer
,
A.
Grupp
,
H.
Nebenführ
, and
M.
Mehring
,
Chem. Phys. Lett.
132
,
279
(
1986
).
61.
P.
Hofer
,
J. Magn. Reson., Ser. A
111
,
77
(
1994
).
62.
S.
Stoll
and
A.
Schweiger
,
J. Magn. Reson.
178
,
42
(
2006
).
63.
M. W.
Anderson
and
L.
Kevan
,
J. Chem. Phys.
87
,
1
(
1987
).
64.
F.
Neese
,
Wiley Interdiscip. Rev.: Comput. Mol. Sci.
2
,
73
(
2012
).
65.
C.
Lee
,
W.
Yang
, and
R. G.
Parr
,
Phys. Rev. B
37
,
785
(
1988
).
66.
A. D.
Becke
,
J. Chem. Phys.
98
,
5648
(
1993
).
67.
A.
Schäfer
,
H.
Horn
, and
R.
Ahlrichs
,
J. Chem. Phys.
97
,
2571
(
1992
).
68.
F.
Weigend
and
R.
Ahlrichs
,
Phys. Chem. Chem. Phys.
7
,
3297
(
2005
).
69.
M.
Ernzerhof
and
G. E.
Scuseria
,
J. Chem. Phys.
110
,
5029
(
1999
).
70.
C.
Adamo
and
V.
Barone
,
J. Chem. Phys.
110
,
6158
(
1999
).
71.
C.
Adamo
,
M.
Cossi
, and
V.
Barone
,
J. Mol. Struct.: THEOCHEM
493
,
145
(
1999
).
72.
A.
Mavrandonakis
,
K. D.
Vogiatzis
,
A. D.
Boese
,
K.
Fink
,
T.
Heine
, and
W.
Klopper
,
Inorg. Chem.
54
,
8251
(
2015
).
73.
S.
Grimme
,
S.
Ehrlich
, and
L.
Goerigk
,
J. Comput. Chem.
32
,
1456
(
2011
).
74.
S.
Grimme
,
J.
Antony
,
S.
Ehrlich
, and
H.
Krieg
,
J. Chem. Phys.
132
,
154104
(
2010
).
75.
W.
Kutzelnigg
,
U.
Fleischer
, and
M.
Schindler
,
Deuterium and Shift Calculation
, edited by
U.
Fleischer
,
W.
Kutzelnigg
,
H.-H.
Limbach
,
G. J.
Martin
,
M. L.
Martin
, and
M.
Schindler
(
Springer Berlin Heidelberg
,
Berlin, Heidelberg
,
1991
), pp.
165
262
.
76.
V.
Barone
, in
Recent Advances in Density Functional Methods. Part I
, edited by
D. P.
Chong
(
World Scientific
,
1995
).
77.
D. E.
Woon
and
T. H.
Dunning
,
J. Chem. Phys.
98
,
1358
(
1993
).
78.
P. F.
Provasi
and
S. P. A.
Sauer
,
J. Chem. Phys.
133
,
54308
(
2010
).
79.
E. D.
Hedegard
,
J.
Kongsted
, and
S. P. A.
Sauer
,
Phys. Chem. Chem. Phys.
14
,
10669
(
2012
).
80.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
81.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
78
,
1396
(
1997
).
82.
A. D.
Becke
,
Phys. Rev. A
38
,
3098
(
1988
).
83.
J. P.
Perdew
,
Phys. Rev. B
33
,
8822
(
1986
).
84.
A. J.
Cohen
and
N. C.
Handy
,
Mol. Phys.
99
,
607
(
2001
).
85.
N. C.
Handy
and
A. J.
Cohen
,
Mol. Phys.
99
,
403
(
2001
).
86.
J. P.
Perdew
,
J. A.
Chevary
,
S. H.
Vosko
,
K. A.
Jackson
,
M. R.
Pederson
,
D. J.
Singh
, and
C.
Fiolhais
,
Phys. Rev. B
46
,
6671
(
1992
).
87.
J.
Tao
,
J. P.
Perdew
,
V. N.
Staroverov
, and
G. E.
Scuseria
,
Phys. Rev. Lett.
91
,
146401
(
2003
).
88.
J. P.
Perdew
,
Phys. Rev. B
34
,
7406
(
1986
).
89.
J. P.
Perdew
and
W.
Yue
,
Phys. Rev. B
33
,
8800
(
1986
).
90.
S. F.
Boys
and
F.
Bernardi
,
Mol. Phys.
19
,
553
(
2006
).
91.
S. A.
Dikanov
,
A. M.
Tyryshkin
, and
M. K.
Bowman
,
J. Magn. Reson.
144
,
228
(
2000
).
92.
R. I.
Samoilova
,
S. A.
Dikanov
,
A. V.
Fionov
,
A. M.
Tyryshkin
,
E. V.
Lunina
, and
M. K.
Bowman
,
J. Phys. Chem.
100
,
17621
(
1996
).
93.
C.
Gemperle
and
A.
Schweiger
,
Chem. Rev.
91
,
1481
(
1991
).
94.
T.
Rudolf
,
A.
Pöppl
,
W.
Brunner
, and
D.
Michel
,
Magn. Reson. Chem.
37
,
S93
S99
(
1999
).
95.
F.
Jensen
,
Introduction to Computational Chemistry
(
John Wiley & Sons
,
Chichester, England, Hoboken, NJ
,
2007
).
96.
R.
Li
,
Z.
Li
, and
Y.
Pan
,
Phys. Chem. Miner.
39
,
491
(
2012
).
97.
L.
Hermosilla
,
P.
Calle
,
J. M.
Garcia de la Vega
, and
C.
Sieiro
,
J. Phys. Chem. A
109
,
1114
(
2005
).
98.
A. C.
Saladino
and
S. C.
Larsen
,
J. Phys. Chem. A
107
,
1872
(
2003
).
99.
M.
Sundararajan
and
F.
Neese
,
J. Chem. Theory Comput.
8
,
563
(
2011
).
100.
J. R.
Morton
and
K. F.
Preston
,
J. Magn. Reson. (1969)
30
,
577
(
1978
).
101.
J. H.
Enemark
and
R. D.
Feltham
,
Coord. Chem. Rev.
13
,
339
(
1974
).
102.
C. E.
Dinerman
and
G. E.
Ewing
,
J. Chem. Phys.
53
,
626
(
1970
).
103.
H.
Yahiro
,
A.
Lund
, and
M.
Shiotani
,
Spectrochim. Acta, Part A
60
,
1267
(
2004
).
104.
T.
Rudolf
,
A.
Pöppl
,
W.
Hofbauer
, and
D.
Michel
,
Phys. Chem. Chem. Phys.
3
,
2167
(
2001
).
105.
106.
P.
Wu
,
Q.
Kan
,
X.
Wang
,
D.
Wang
,
H.
Xing
,
P.
Yang
, and
T.
Wu
,
Appl. Catal., A
282
,
39
(
2005
).

Supplementary Material

You do not currently have access to this content.