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‘Ionic crystals’ consisting of trinuclear macrocations and polyoxometalate anions exhibiting single crystal to single crystal transformation: breathing of crystals
Ion pairing of trinuclear macrocation cluster (known as basic carboxylate), [ M 3 ( μ 3 -O) ( ClCH 2 COO ) 6 ( H 2 O ) 3 ] 1 + and a Keggin type polyoxometalate cluster anion [ SiW 12 O 40 ] 4 - is stabilized with a number of crystal water molecules in composite type compounds [ M 3 ( μ 3 -O) ( ClCH...
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| Published in: | Journal of chemical sciences (Bangalore, India) India), 2017-08, Vol.129 (8), p.1121-1142 |
|---|---|
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| container_end_page | 1142 |
| container_issue | 8 |
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| container_title | Journal of chemical sciences (Bangalore, India) |
| container_volume | 129 |
| creator | Arumuganathan, T Siddikha, Asha Das, Samar K |
| description | Ion pairing of trinuclear macrocation cluster (known as basic carboxylate), [
M
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
1
+
and a Keggin type polyoxometalate cluster anion
[
SiW
12
O
40
]
4
-
is stabilized with a number of crystal water molecules in composite type compounds [
M
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
xH
2
O
·
2ClCH
2
COOH
[
M
=
Fe
3
+
,
x
=
18
(
1
)
;
M
=
Cr
3
+
x
=
14
(
2
)
]. When the crystals of
1
are heated at 85
∘
C and 135
∘
C for 3.5 hours in an open atmospheric condition, it goes to [
Fe
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
10
H
2
O
·
2ClCH
2
COOH (
dehydrated
1
-
85
o
≡
1
′
), and [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
8
H
2
O
·
2
ClCH
2
COOH (
dehydrated 1
-
135
o
≡
1
″
) respectively with the loss of considerable amount of lattice water molecules retaining their single crystallinity. On the other hand, the single crystals of compound
2
, upon heating at 85
∘
C or 135
∘
C for 3.5 hours, undergo ‘crystal-to-crystal transformation’ to the single crystals of [
Cr
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
8
H
2
O
·
2
ClCH
2
COOH (
dehydrated
2
≡
2
′
). Crystal structure analyses show that the parent compounds
1
and
2
undergo molecular rearrangement (molecular motion in the solid state) in respective dehydrated compounds. Remarkably, these dehydrated crystals (
1
′
,
1
″
and
2
′
), upon exposure to water vapor at an ambient condition, regenerate the crystals of parent compounds
1
and
2
, respectively.
Graphical Abstract:
Breathing of crystal:
The unit cell volume (17106 Å
3
)
of [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
18
H
2
O
·
2
ClCH
2
COOH (
1
) shrinks on heating
1
at 85
∘
C to produce the reduced unit cell volume (15084 Å
3
) of [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
10
H
2
O
·
2
ClCH
2
COOH (
dehydrated 1
-
85
o
), represented as (a)
→
(b). This can be reversed, (b)
→
(a), in the solid state on re-hydration of
dehydrated 1
-
85
o
resulting in the formation of parent
1
. |
| doi_str_mv | 10.1007/s12039-017-1324-0 |
| format | article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_1929476742</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1929476742</sourcerecordid><originalsourceid>FETCH-LOGICAL-c425t-448d46e5dd4c08c54be1ac492eea73eb290ff24551ea64caca9348f066e275cf3</originalsourceid><addsrcrecordid>eNp1kU1OwzAQhSMEEqVwAHaWWAf8l7hhhyp-KlViA2vLcSZtqiQutiu1ux4DTsC9ehLcpJWQEBuPNX7vm5FfFF0TfEswFneOUMyyGBMRE0Z5jE-iAc4EiwXB7LS785ilND2PLpxbYMxGXLBB9L3bfk5MW2mk7cZ5Vbvd9gtp07rK-aqdIVMib6t2pWtQFjVKW6OVr4IAqbZAS1NvzNo0EKzKQ-h1T7CeV3nVAVw4ajjikTd_Ola1rjS26bD3KLeg_Pww-7jVZXRWhgJXhzqM3p8e38Yv8fT1eTJ-mMaa08THnI8KnkJSFFzjkU54DkRpnlEAJRjkNMNlSXmSEFAp10qrjPFRidMUqEh0yYbRTc9dWvOxAuflwqxsG0ZKktGMi1RwGlSkV4XfcM5CKZe2apTdSILlPg_Z5yFDHnKfh8TBQ3uPC9p2BvYX-V_TD4D2lYg</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1929476742</pqid></control><display><type>article</type><title>‘Ionic crystals’ consisting of trinuclear macrocations and polyoxometalate anions exhibiting single crystal to single crystal transformation: breathing of crystals</title><source>Springer Nature</source><source>Free Full-Text Journals in Chemistry</source><creator>Arumuganathan, T ; Siddikha, Asha ; Das, Samar K</creator><creatorcontrib>Arumuganathan, T ; Siddikha, Asha ; Das, Samar K</creatorcontrib><description>Ion pairing of trinuclear macrocation cluster (known as basic carboxylate), [
M
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
1
+
and a Keggin type polyoxometalate cluster anion
[
SiW
12
O
40
]
4
-
is stabilized with a number of crystal water molecules in composite type compounds [
M
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
xH
2
O
·
2ClCH
2
COOH
[
M
=
Fe
3
+
,
x
=
18
(
1
)
;
M
=
Cr
3
+
x
=
14
(
2
)
]. When the crystals of
1
are heated at 85
∘
C and 135
∘
C for 3.5 hours in an open atmospheric condition, it goes to [
Fe
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
10
H
2
O
·
2ClCH
2
COOH (
dehydrated
1
-
85
o
≡
1
′
), and [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
8
H
2
O
·
2
ClCH
2
COOH (
dehydrated 1
-
135
o
≡
1
″
) respectively with the loss of considerable amount of lattice water molecules retaining their single crystallinity. On the other hand, the single crystals of compound
2
, upon heating at 85
∘
C or 135
∘
C for 3.5 hours, undergo ‘crystal-to-crystal transformation’ to the single crystals of [
Cr
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
8
H
2
O
·
2
ClCH
2
COOH (
dehydrated
2
≡
2
′
). Crystal structure analyses show that the parent compounds
1
and
2
undergo molecular rearrangement (molecular motion in the solid state) in respective dehydrated compounds. Remarkably, these dehydrated crystals (
1
′
,
1
″
and
2
′
), upon exposure to water vapor at an ambient condition, regenerate the crystals of parent compounds
1
and
2
, respectively.
Graphical Abstract:
Breathing of crystal:
The unit cell volume (17106 Å
3
)
of [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
18
H
2
O
·
2
ClCH
2
COOH (
1
) shrinks on heating
1
at 85
∘
C to produce the reduced unit cell volume (15084 Å
3
) of [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
10
H
2
O
·
2
ClCH
2
COOH (
dehydrated 1
-
85
o
), represented as (a)
→
(b). This can be reversed, (b)
→
(a), in the solid state on re-hydration of
dehydrated 1
-
85
o
resulting in the formation of parent
1
.</description><identifier>ISSN: 0974-3626</identifier><identifier>EISSN: 0973-7103</identifier><identifier>DOI: 10.1007/s12039-017-1324-0</identifier><language>eng</language><publisher>New Delhi: Springer India</publisher><subject>Anions ; Breathing ; Chain dynamics ; Chemistry ; Chemistry and Materials Science ; Chemistry/Food Science ; Clusters ; Crystal structure ; Crystallinity ; Dehydration ; Heating ; Hydration ; Ionic crystals ; Molecular motion ; Regular Article ; Single crystals ; Solid state ; Transformations ; Unit cell ; Water chemistry ; Water vapor</subject><ispartof>Journal of chemical sciences (Bangalore, India), 2017-08, Vol.129 (8), p.1121-1142</ispartof><rights>Indian Academy of Sciences 2017</rights><rights>Copyright Springer Science & Business Media 2017</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c425t-448d46e5dd4c08c54be1ac492eea73eb290ff24551ea64caca9348f066e275cf3</citedby><cites>FETCH-LOGICAL-c425t-448d46e5dd4c08c54be1ac492eea73eb290ff24551ea64caca9348f066e275cf3</cites><orcidid>0000-0002-9536-6579</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Arumuganathan, T</creatorcontrib><creatorcontrib>Siddikha, Asha</creatorcontrib><creatorcontrib>Das, Samar K</creatorcontrib><title>‘Ionic crystals’ consisting of trinuclear macrocations and polyoxometalate anions exhibiting single crystal to single crystal transformation: breathing of crystals</title><title>Journal of chemical sciences (Bangalore, India)</title><addtitle>J Chem Sci</addtitle><description>Ion pairing of trinuclear macrocation cluster (known as basic carboxylate), [
M
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
1
+
and a Keggin type polyoxometalate cluster anion
[
SiW
12
O
40
]
4
-
is stabilized with a number of crystal water molecules in composite type compounds [
M
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
xH
2
O
·
2ClCH
2
COOH
[
M
=
Fe
3
+
,
x
=
18
(
1
)
;
M
=
Cr
3
+
x
=
14
(
2
)
]. When the crystals of
1
are heated at 85
∘
C and 135
∘
C for 3.5 hours in an open atmospheric condition, it goes to [
Fe
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
10
H
2
O
·
2ClCH
2
COOH (
dehydrated
1
-
85
o
≡
1
′
), and [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
8
H
2
O
·
2
ClCH
2
COOH (
dehydrated 1
-
135
o
≡
1
″
) respectively with the loss of considerable amount of lattice water molecules retaining their single crystallinity. On the other hand, the single crystals of compound
2
, upon heating at 85
∘
C or 135
∘
C for 3.5 hours, undergo ‘crystal-to-crystal transformation’ to the single crystals of [
Cr
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
8
H
2
O
·
2
ClCH
2
COOH (
dehydrated
2
≡
2
′
). Crystal structure analyses show that the parent compounds
1
and
2
undergo molecular rearrangement (molecular motion in the solid state) in respective dehydrated compounds. Remarkably, these dehydrated crystals (
1
′
,
1
″
and
2
′
), upon exposure to water vapor at an ambient condition, regenerate the crystals of parent compounds
1
and
2
, respectively.
Graphical Abstract:
Breathing of crystal:
The unit cell volume (17106 Å
3
)
of [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
18
H
2
O
·
2
ClCH
2
COOH (
1
) shrinks on heating
1
at 85
∘
C to produce the reduced unit cell volume (15084 Å
3
) of [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
10
H
2
O
·
2
ClCH
2
COOH (
dehydrated 1
-
85
o
), represented as (a)
→
(b). This can be reversed, (b)
→
(a), in the solid state on re-hydration of
dehydrated 1
-
85
o
resulting in the formation of parent
1
.</description><subject>Anions</subject><subject>Breathing</subject><subject>Chain dynamics</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Chemistry/Food Science</subject><subject>Clusters</subject><subject>Crystal structure</subject><subject>Crystallinity</subject><subject>Dehydration</subject><subject>Heating</subject><subject>Hydration</subject><subject>Ionic crystals</subject><subject>Molecular motion</subject><subject>Regular Article</subject><subject>Single crystals</subject><subject>Solid state</subject><subject>Transformations</subject><subject>Unit cell</subject><subject>Water chemistry</subject><subject>Water vapor</subject><issn>0974-3626</issn><issn>0973-7103</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNp1kU1OwzAQhSMEEqVwAHaWWAf8l7hhhyp-KlViA2vLcSZtqiQutiu1ux4DTsC9ehLcpJWQEBuPNX7vm5FfFF0TfEswFneOUMyyGBMRE0Z5jE-iAc4EiwXB7LS785ilND2PLpxbYMxGXLBB9L3bfk5MW2mk7cZ5Vbvd9gtp07rK-aqdIVMib6t2pWtQFjVKW6OVr4IAqbZAS1NvzNo0EKzKQ-h1T7CeV3nVAVw4ajjikTd_Ola1rjS26bD3KLeg_Pww-7jVZXRWhgJXhzqM3p8e38Yv8fT1eTJ-mMaa08THnI8KnkJSFFzjkU54DkRpnlEAJRjkNMNlSXmSEFAp10qrjPFRidMUqEh0yYbRTc9dWvOxAuflwqxsG0ZKktGMi1RwGlSkV4XfcM5CKZe2apTdSILlPg_Z5yFDHnKfh8TBQ3uPC9p2BvYX-V_TD4D2lYg</recordid><startdate>20170801</startdate><enddate>20170801</enddate><creator>Arumuganathan, T</creator><creator>Siddikha, Asha</creator><creator>Das, Samar K</creator><general>Springer India</general><general>Springer Nature B.V</general><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-9536-6579</orcidid></search><sort><creationdate>20170801</creationdate><title>‘Ionic crystals’ consisting of trinuclear macrocations and polyoxometalate anions exhibiting single crystal to single crystal transformation: breathing of crystals</title><author>Arumuganathan, T ; Siddikha, Asha ; Das, Samar K</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c425t-448d46e5dd4c08c54be1ac492eea73eb290ff24551ea64caca9348f066e275cf3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Anions</topic><topic>Breathing</topic><topic>Chain dynamics</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Chemistry/Food Science</topic><topic>Clusters</topic><topic>Crystal structure</topic><topic>Crystallinity</topic><topic>Dehydration</topic><topic>Heating</topic><topic>Hydration</topic><topic>Ionic crystals</topic><topic>Molecular motion</topic><topic>Regular Article</topic><topic>Single crystals</topic><topic>Solid state</topic><topic>Transformations</topic><topic>Unit cell</topic><topic>Water chemistry</topic><topic>Water vapor</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Arumuganathan, T</creatorcontrib><creatorcontrib>Siddikha, Asha</creatorcontrib><creatorcontrib>Das, Samar K</creatorcontrib><collection>CrossRef</collection><jtitle>Journal of chemical sciences (Bangalore, India)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Arumuganathan, T</au><au>Siddikha, Asha</au><au>Das, Samar K</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>‘Ionic crystals’ consisting of trinuclear macrocations and polyoxometalate anions exhibiting single crystal to single crystal transformation: breathing of crystals</atitle><jtitle>Journal of chemical sciences (Bangalore, India)</jtitle><stitle>J Chem Sci</stitle><date>2017-08-01</date><risdate>2017</risdate><volume>129</volume><issue>8</issue><spage>1121</spage><epage>1142</epage><pages>1121-1142</pages><issn>0974-3626</issn><eissn>0973-7103</eissn><abstract>Ion pairing of trinuclear macrocation cluster (known as basic carboxylate), [
M
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
1
+
and a Keggin type polyoxometalate cluster anion
[
SiW
12
O
40
]
4
-
is stabilized with a number of crystal water molecules in composite type compounds [
M
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
xH
2
O
·
2ClCH
2
COOH
[
M
=
Fe
3
+
,
x
=
18
(
1
)
;
M
=
Cr
3
+
x
=
14
(
2
)
]. When the crystals of
1
are heated at 85
∘
C and 135
∘
C for 3.5 hours in an open atmospheric condition, it goes to [
Fe
3
(
μ
3
-O)
(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
10
H
2
O
·
2ClCH
2
COOH (
dehydrated
1
-
85
o
≡
1
′
), and [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
8
H
2
O
·
2
ClCH
2
COOH (
dehydrated 1
-
135
o
≡
1
″
) respectively with the loss of considerable amount of lattice water molecules retaining their single crystallinity. On the other hand, the single crystals of compound
2
, upon heating at 85
∘
C or 135
∘
C for 3.5 hours, undergo ‘crystal-to-crystal transformation’ to the single crystals of [
Cr
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
8
H
2
O
·
2
ClCH
2
COOH (
dehydrated
2
≡
2
′
). Crystal structure analyses show that the parent compounds
1
and
2
undergo molecular rearrangement (molecular motion in the solid state) in respective dehydrated compounds. Remarkably, these dehydrated crystals (
1
′
,
1
″
and
2
′
), upon exposure to water vapor at an ambient condition, regenerate the crystals of parent compounds
1
and
2
, respectively.
Graphical Abstract:
Breathing of crystal:
The unit cell volume (17106 Å
3
)
of [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
18
H
2
O
·
2
ClCH
2
COOH (
1
) shrinks on heating
1
at 85
∘
C to produce the reduced unit cell volume (15084 Å
3
) of [
Fe
3
(
μ
3
-O)(
ClCH
2
COO
)
6
(
H
2
O
)
3
]
4
[
SiW
12
O
40
]
·
10
H
2
O
·
2
ClCH
2
COOH (
dehydrated 1
-
85
o
), represented as (a)
→
(b). This can be reversed, (b)
→
(a), in the solid state on re-hydration of
dehydrated 1
-
85
o
resulting in the formation of parent
1
.</abstract><cop>New Delhi</cop><pub>Springer India</pub><doi>10.1007/s12039-017-1324-0</doi><tpages>22</tpages><orcidid>https://orcid.org/0000-0002-9536-6579</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0974-3626 |
| ispartof | Journal of chemical sciences (Bangalore, India), 2017-08, Vol.129 (8), p.1121-1142 |
| issn | 0974-3626 0973-7103 |
| language | eng |
| recordid | cdi_proquest_journals_1929476742 |
| source | Springer Nature; Free Full-Text Journals in Chemistry |
| subjects | Anions Breathing Chain dynamics Chemistry Chemistry and Materials Science Chemistry/Food Science Clusters Crystal structure Crystallinity Dehydration Heating Hydration Ionic crystals Molecular motion Regular Article Single crystals Solid state Transformations Unit cell Water chemistry Water vapor |
| title | ‘Ionic crystals’ consisting of trinuclear macrocations and polyoxometalate anions exhibiting single crystal to single crystal transformation: breathing of crystals |
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