Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
“On-off-on” fluorescent indicators of pH windows based on three
separated components
P. Pallavicini, V. Amendola, C. Massera, E. C. Mundum, A. Taglietti
Supporting Information
(Pages 16 including top sheet)
Table SI
Crystal data of [Cu(tcq)Cl]CF3SO3·1.5H2O
pp 2
Table SII
Table SIII
Table SIV
Table SV
Figure SI
Figure SII
Figure SIII
Figure SIV
Figure SV
Figure SVI
Atomic coordinates of non-H atoms of [Cu(tcq)Cl]CF3SO3·1.5H2O
pp 4
Anisotropic coefficients of non-H atoms of [Cu(tcq)Cl]CF3SO3·1.5H2O
pp 5
Atomic coordinates of H atoms of [Cu(tcq)Cl]CF3SO3·1.5H2O
pp 6
Listing of bond lengths (Å) and angles (deg) of [Cu(tcq)Cl]CF3SO3·1.5H2O
pp 7
Molecular structure of [Cu(tcq)Cl]CF3SO3·1.5H2O
pp 9
distribution diagram (% of species vs pH) for 1:1 tcq/Cu2+
pp 10
2+
distribution diagram (% of species vs pH) for 1:1 ccq/Cu
pp 11
titration profile (emf vs ml of added base) for tcq plus excess acid
pp 12
titration profile (emf vs ml of added base) for ccq plus excess acid
pp 13
titration profile (emf vs ml of added base) for tcq plus 1:1 Cu2+ plus excess acid pp 14
Figure SVII titration profile (emf vs ml of added base) for ccq plus 1:1 Cu2+ plus excess acid pp 15
Figure SVIII emission spectra recorded by pH variation for Coumarine 343
pp 16
In the potentiometric and spectrophotometric experiments, samples of pure ligands were
used, prepared by redissolution of the ammonium salts in 0.1 M NaOH, followed by
extraction with CH2Cl2, drying over MgSO4, removal of dessicant and solvent, and highvacuum treatment (<0.1 Torr). Titrations were carried out on solutions of dioxane-water (4
: 1 v/v) with 0.1 M KNO3 as the background electrolyte. Cu(CF3SO3)2 was used as the
copper
salt.
EMF
vs.
volume
of
added
base
profiles
are
provided.
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Table SI. Crystal data of [Cu(tcq)Cl]CF3SO3·1.5H2O
Formula
fw
Crystal system
Space group
a, Å
b, Å
c, Å
, deg
V, Å3
Z
calcd, g cm-3
, mm-1
F(000)
Crystal size, mm3
range, deg
Limiting indices
Reflns collected
Independent reflns
C27H28ClCuF3N4O3S·1.5H2O
671.61
Monoclinic
C2
29.723(5)
8.506(5)
11.882(5)
94.33(1)
2995(2)
4
1.489
0.948
1384
0.22 x 0.15 x 0.28
1.37 to 27.03
-35h37, -10k10, -15l10
10133
6368 (Rint = 0.0494)
Obs. reflns [I>2(I)]
Data / restr. / param.
2777
6368 / 1 / 379
Goodness-of-fit on F2
0.610
Final R indices [I>2(I)]
R indices (all data)
Largest diff. peak and hole, eÅ-3
R1 = 0.0492, wR2 = 0.1038
R1 = 0.1355, wR2 = 0.1316
0.329 and -0.193 ^-3^M
R1 = ||Fo|-|Fc||/| |Fo|
wR2 = [[w(Fo2-Fc2)2/w(Fo2)2]1/2
Intensity data and cell parameters were recorded at room temperature (25°C) on a
Bruker AXS Smart 1000 single-crystal diffractometer (MoK radiation) equipped
with a CCD area detector, and automatically corrected for absorption using
“SMART” software.
The structure was solved by Patterson using the SHELXS-97 program [A] and
refined on F2 by full-matrix least-squares using the SHELXL-97 program [A]. All
non-hydrogen atoms were refined with anisotropic atomic displacements, while the
hydrogen atoms were introduced into the geometrically calculated positions and
refined “riding” on the corresponding parent atoms. The weighting scheme used in
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
the last cycle of refinement was w = 1/ [2Fo2 + (0.0837P)2] where P = (Fo2 +
2Fc2)/3. Molecular geometry calculations were carried out using the PARST97
program [B]. Drawings were obtained by ORTEP3 in the WinGX suite [C]. All
calculations were carried out on a DIGITAL Alpha Station 255 computer.
[A] G. M. Sheldrick, SHELX-97, Program for Crystal Structure Refinement,
University of Göttingen, 1997; http://shelx.uni-ac.gwdg.de/shelx/index.html.
[B] M. Nardelli, PARST97, updated version of PARST95, J. Appl. Crystallogr.,
1995, 28, 659.
[C] Ortep3 in the WinGX suite, L.J. Farrugia, J. Appl. Crystallogr., 1997, 30, 565.
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Table SII. Fractional Atomic Coordinates (x104) and
Equivalent Isotropic Thermal Parameters (Å2x104) with
E.s.d.'s in Parentheses for [Cu(tcq)Cl]CF3SO3·1.5H2O.
Atom
Cu
S
Cl
N1
N2
N3
N4
F1
F2
F3
O1
O2
O3
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
O1S
O2S
X/a
6087.5(2)
6069.5(6)
6154.9(6)
6115(2)
5716(1)
5909(2)
6743(2)
6935(2)
6626(2)
6632(2)
6095(2)
6114(2)
5727(2)
5442(2)
5237(2)
4992(2)
5294(2)
5489(2)
5740(2)
5466(2)
5776(2)
5721(2)
6006(2)
6374(2)
6421(2)
6786(2)
7091(2)
7056(2)
6706(2)
6284(2)
6732(2)
7120(3)
7522(3)
7552(2)
7145(2)
7158(2)
7555(2)
7954(2)
7953(2)
6578(3)
5441(2)
5000(0)
Y/b
5173.4(8)
6884.2(24)
3482.0(21)
3528(6)
6300(6)
6983(6)
6528(5)
6714(8)
4589(7)
5454(9)
7152(8)
8253(7)
5829(8)
7517(7)
8719(8)
9996(10)
10760(8)
9579(8)
8263(7)
5082(9)
3712(7)
2714(8)
1502(8)
1281(7)
2335(6)
2154(7)
983(8)
-35(9)
91(9)
7443(9)
7331(7)
8046(8)
7881(9)
7054(8)
6416(7)
5660(7)
5487(9)
6058(10)
6854(9)
5838(12)
4031(12)
5799(10)
Z/c
3260.6(5)
-1215.2(19)
4747.5(15)
2007(4)
2025(4)
4232(4)
3563(4)
-1091(6)
-794(6)
-2440(4)
-49(5)
-1858(6)
-1580(6)
2528(5)
1696(6)
2267(7)
3205(7)
4023(6)
3460(5)
1371(5)
1204(5)
296(6)
181(5)
992(5)
1904(5)
2718(5)
2595(6)
1694(6)
911(6)
5021(6)
4511(5)
5038(5)
4586(6)
3587(6)
3071(5)
2034(5)
1548(6)
2076(7)
3050(7)
-1408(8)
6626(7)
5000(0)
Ueq
527(2)
808(8)
732(7)
479(16)
489(17)
585(18)
510(17)
1484(30)
1468(30)
1534(29)
1238(28)
1281(30)
1311(31)
538(21)
708(26)
877(29)
838(32)
773(29)
558(21)
618(20)
495(20)
640(25)
645(25)
550(22)
496(21)
594(23)
687(26)
700(26)
686(23)
772(30)
549(22)
706(27)
725(28)
637(25)
531(21)
603(24)
818(30)
874(32)
790(30)
909(36)
1827(42)
1539(49)
Equivalent Isotropic U defined as one-third of the race
of the orthogonalized Uij tensor.
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Table SIII. Anisotropic Thermal Parameters(x104) with
E.s.d.'s in parentheses for the non-Hydrogen Atoms of
[Cu(tcq)Cl]CF3SO3·1.5H2O.They are in the form:
xp(-22(U11h2a*2+...+2U12hka*b*+...))
Atom
Cu
S
N1
N2
N3
N4
F1
F2
F3
O1
Cl
O2
O3
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
O1S
O2S
U11
542(4)
792(13)
474(26)
419(26)
606(31)
502(28)
752(31)
1486(49)
1705(46)
1522(51)
868(12)
1255(47)
839(34)
411(31)
544(37)
683(39)
749(46)
729(46)
439(31)
453(28)
466(32)
565(39)
686(41)
605(37)
557(34)
622(38)
735(44)
726(41)
735(38)
891(55)
675(40)
1048(58)
699(45)
613(42)
510(35)
502(34)
769(45)
592(45)
487(40)
900(60)
1188(48)
1704(81)
U22
549(4)
761(14)
475(29)
561(30)
636(33)
543(32)
1559(52)
1102(47)
2038(68)
1301(51)
752(12)
1121(49)
1558(68)
572(38)
702(46)
650(45)
526(42)
696(49)
581(38)
713(38)
546(37)
735(46)
690(47)
534(38)
437(36)
548(40)
505(37)
573(47)
476(34)
873(57)
465(36)
561(41)
809(51)
564(40)
513(36)
659(49)
781(60)
1126(61)
947(57)
950(61)
2422(91)
1106(72)
U33
U23
485(4)
-34(5)
889(15) -107(12)
486(28)
-4(24)
492(29)
0(25)
522(32)
-65(28)
479(30)
-97(25)
2156(67)
-36(50)
1822(57)
437(42)
895(33) -183(42)
982(43) -435(38)
574(11)
110(9)
1516(57)
377(45)
1500(55) -561(46)
645(40)
54(33)
858(49)
128(40)
1305(62)
83(55)
1240(70) -130(44)
928(54)
-43(41)
671(41)
33(34)
673(37) -113(45)
467(35)
-6(31)
603(43) -114(37)
557(42)
-84(35)
515(37)
0(32)
503(37)
44(29)
591(40)
-39(32)
809(51)
85(37)
807(46)
39(43)
873(46) -155(49)
537(43) -153(39)
487(37)
-21(30)
466(38)
-52(31)
627(47)
0(42)
710(47)
146(37)
563(38)
13(30)
651(40)
-55(32)
924(50)
-88(42)
918(59)
50(52)
911(57)
115(49)
908(64)
104(55)
1900(73) -1016(71)
1971(99)
0(0)
U13
U12
-6(3)
184(12)
20(24)
60(23)
109(27)
-14(24)
208(37)
156(45)
329(33)
686(39)
42(10)
423(43)
-155(34)
129(30)
-72(35)
107(42)
85(48)
288(42)
160(31)
-51(27)
-4(30)
-67(33)
40(36)
69(32)
95(30)
-92(34)
-25(39)
102(37)
222(36)
-36(41)
-90(32)
-228(41)
-231(43)
-97(37)
-11(31)
51(31)
197(41)
149(44)
-116(41)
269(53)
296(51)
1215(78)
26(5)
61(11)
-62(25)
-29(24)
11(28)
-11(24)
71(35)
382(35)
837(50)
-355(43)
79(11)
474(41)
-30(37)
-40(29)
27(36)
160(47)
62(35)
58(36)
35(30)
61(42)
-84(30)
-101(36)
-94(37)
-140(33)
-47(31)
-5(33)
44(37)
17(42)
-38(45)
88(43)
-27(31)
-38(40)
-106(38)
-57(33)
-49(28)
-97(29)
-149(42)
-95(43)
-166(38)
45(50)
-350(54)
0(0)
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Table SIV. Fractional Atomic Coordinates (x104) and
Isotropic Thermal Parameters (x104) with E.s.d.'s in
parentheses
for
the
Hydrogen
Atoms
in
[Cu(tcq)Cl]CF3SO3·1.5H2O.
Atom
H1
H2
H3
H2A
H2B
H3A
H3B
H4A
H4B
H5A
H5B
H6
H7A
H7B
H9
H10
H13
H14
H15
H16
H17A
H17B
H19
H20
H23
H24
H25
H26
X/a
5194(0)
5906(0)
5678(0)
5474(0)
5028(0)
4727(0)
4892(0)
5536(0)
5119(0)
5248(0)
5696(0)
5999(0)
5353(0)
5210(0)
5483(0)
5962(0)
6819(0)
7330(0)
7274(0)
6681(0)
6290(0)
6239(0)
7101(0)
7780(0)
6893(0)
7559(0)
8225(0)
8221(0)
Y/b
6988(0)
6780(0)
6660(0)
9183(0)
8193(0)
9559(0)
10787(0)
11321(0)
11518(0)
9125(0)
10102(0)
8729(0)
5500(0)
4737(0)
2875(0)
817(0)
2828(0)
868(0)
-808(0)
-611(0)
6772(0)
8516(0)
8628(0)
8325(0)
5270(0)
4982(0)
5886(0)
7278(0)
Z/c
2874(0)
1569(0)
4637(0)
1288(0)
1153(0)
2582(0)
1716(0)
2877(0)
3599(0)
4425(0)
4571(0)
3122(0)
644(0)
1769(0)
-247(0)
-428(0)
3334(0)
3138(0)
1625(0)
310(0)
5682(0)
5265(0)
5695(0)
4947(0)
1671(0)
855(0)
1751(0)
3374(0)
Ueq
438(70)
438(70)
438(70)
830(60)
830(60)
830(60)
830(60)
830(60)
830(60)
830(60)
830(60)
438(70)
830(60)
830(60)
694(50)
694(50)
694(50)
694(50)
694(50)
694(50)
830(60)
830(60)
694(50)
694(50)
694(50)
694(50)
694(50)
694(50)
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Table SV. Complete list of bond distances (Å)
angles (deg) of complex [Cu(tcq)Cl]CF3SO3·1.5H2O.
Cu-N1
Cu-N2
Cu-N3
Cu-N4
Cu-Cl
S-O1
S-O2
S-O3
S-C27
N1-C8
N1-C12
N2-C1
N2-C7
N3-C6
N3-C17
N4-C18
N4-C22
F1-C27
F2-C27
F3-C27
C1-C2
C1-C6
C2-C3
C3-C4
C4-C5
C5-C6
C7-C8
C8-C9
C9-C10
C10-C11
C11-C12
C11-C16
C12-C13
C13-C14
C14-C15
C15-C16
C17-C18
C18-C19
C19-C20
C20-C21
C21-C22
C21-C26
C22-C23
C23-C24
C24-C25
C25-C26
N1-Cu-N4
N1-Cu-Cl
N2-Cu-N3
N2-Cu-N1
N2-Cu-N4
N2-Cu-Cl
N3-Cu-N1
N3-Cu-N4
N3-Cu-Cl
N4-Cu-Cl
O1-S-O2
O1-S-O3
O1-S-C27
2.050(5)
2.013(5)
2.019(5)
2.269(5)
2.276(2)
1.401(6)
1.405(7)
1.401(6)
1.784(9)
1.343(7)
1.374(7)
1.471(8)
1.464(8)
1.487(8)
1.455(8)
1.320(8)
1.373(8)
1.328(11)
1.290(12)
1.290(11)
1.518(9)
1.504(8)
1.498(10)
1.522(11)
1.485(10)
1.526(9)
1.508(9)
1.373(9)
1.349(10)
1.415(8)
1.405(8)
1.421(9)
1.407(8)
1.361(9)
1.374(10)
1.347(9)
1.506(10)
1.408(9)
1.353(11)
1.388(10)
1.421(8)
1.405(10)
1.393(9)
1.361(10)
1.385(10)
1.341(12)
112.40(17)
97.28(14)
84.30(19)
81.06(19)
106.94(17)
151.49(14)
164.3(2)
77.36(18)
92.86(15)
100.02(13)
113.8(4)
113.2(4)
103.0(4)
and
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O2-S-O3
O2-S-C27
O3-S-C27
Cu-N1-C8
Cu-N1-C12
C8-N1-C12
Cu-N2-C1
Cu-N2-C7
C1-N2-C7
Cu-N3-C6
Cu-N3-C17
C6-N3-C17
Cu-N4-C18
Cu-N4-C22
C18-N4-C22
N2-C1-C2
N2-C1-C6
C2-C1-C6
C1-C2-C3
C2-C3-C4
C3-C4-C5
C4-C5-C6
N3-C6-C1
N3-C6-C5
C1-C6-C5
N2-C7-C8
N1-C8-C7
N1-C8-C9
C7-C8-C9
C8-C9-C10
C9-C10-C11
C10-C11-C12
C10-C11-C16
C12-C11-C16
N1-C12-C11
N1-C12-C13
C11-C12-C13
C12-C13-C14
C13-C14-C15
C14-C15-C16
C11-C16-C15
N3-C17-C18
N4-C18-C17
N4-C18-C19
C17-C18-C19
C18-C19-C20
C19-C20-C21
C20-C21-C22
C20-C21-C26
C22-C21-C26
N4-C22-C21
N4-C22-C23
C21-C22-C23
C22-C23-C24
C23-C24-C25
C24-C25-C26
C21-C26-C2
S-C27-F1
S-C27-F2
S-C27-F3
F1-C27-F2
F1-C27-F3
F2-C27-F3
117.3(4)
103.2(4)
104.1(4)
111.6(4)
129.2(4)
119.2(5)
109.2(3)
106.2(3)
116.1(5)
107.3(4)
110.6(4)
114.1(5)
108.8(4)
131.4(4)
118.5(5)
114.6(5)
106.5(5)
112.3(5)
112.3(6)
111.2(6)
111.7(6)
112.9(6)
107.4(5)
114.9(5)
110.7(5)
109.1(5)
115.4(5)
121.7(5)
122.9(6)
120.9(6)
119.5(6)
117.8(5)
123.6(6)
118.6(6)
120.8(5)
120.1(5)
119.1(5)
119.4(6)
122.2(6)
119.7(7)
120.9(6)
112.4(6)
117.1(5)
122.1(5)
120.8(6)
119.8(7)
120.5(7)
117.1(6)
124.1(7)
118.8(6)
121.9(5)
119.4(5)
118.6(6)
120.5(6)
120.7(6)
120.7(7)
120.6(7)
110.5(6)
113.4(7)
114.6(7)
104.4(8)
105.0(8)
108.2(8)
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Figure SI. Crystal structure of [Cu(tcq)Cl]CF3SO3·1.5H2O. Water
molecules and CF3SO3 anion have been omitted for clarity
C26
C20
C21
C25
C19
C24
C22
C18
C23
N4
C17
C14
N3
C13
Cl
C15
C12
C16
C6
Cu
N2
N1
C1
C11
C8
C10
C9
C7
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Figure SII. % of species vs pH with respect to total tcq for a
1×10-3 M solution of 1:1 tcq/Cu2+
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Figure SIII. % of species vs pH with respect to total ccq for a 1×10-3
M solution of 1:1 ccq/Cu2+
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Figure SIV. titration profile (emf vs ml of added base) for
ligand tcq plus excess acid
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Figure SV. titration profile (emf vs ml of added base) for ligand
ccq plus excess acid
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Figure SVI. titration profile (emf vs ml of added base) for ligand
tcq plus one equivalent of CuII(CF3SO3)2 plus excess acid
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Figure SVII. titration profile (emf vs ml of added base) for
ligand ccq plus one equivalent of CuII(CF3SO3)2 plus excess acid
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Figure SVIII. emission spectra for Coumarine 343 on pH variation
in dioxane/water 4:1