Multicomponent Platinum(II) Cages with Tunable ... - ACS Publications

Subscriber access provided by HACETTEPE UNIVERSITESI KUTUPHANESI

Article

Multicomponent Platinum(II) Cages with Tunable Emission and Amino Acid Sensing Mingming Zhang, Manik Lal Saha, Ming Wang, Zhixuan Zhou, Bo Song, Chenjie Lu, Xuzhou Yan, Xiaopeng Li, Feihe Huang, Shouchun Yin, and Peter J. Stang J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 23 Mar 2017 Downloaded from http://pubs.acs.org on March 23, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Journal of the American Chemical Society is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Journal of the American Chemical Society

Multicomponent Platinum(II) Cages with Tunable Emission and Amino Acid Sensing Mingming Zhang,∗,† Manik Lal Saha,∗,† Ming Wang,‡ Zhixuan Zhou,† Bo Song,║ Chenjie Lu,§ Xuzhou Yan,† Xiaopeng Li,║ Feihe Huang,⊥ Shouchun Yin,∗,†,§ and Peter J. Stang∗,† †

Department of Chemistry, University of Utah, 315 South 1400 East, Room 2020, Salt Lake City, Utah

84112, United States ‡

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University,

Changchun, Jilin 130012, P.R. China ║

Department of Chemistry, University of South Florida, 4202 East Fowler Ave, Tampa, Florida 33620,

United States §

College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou

310036, P. R. China ⊥

State Key Laboratory of Chemical Engineering, Center for Chemistry of High-Performance & Novel

Materials, Department of Chemistry, Zhejiang University, Hangzhou 310027, P.R. China

Supporting Information

■ABSTRACT The syntheses, characterization and the emission properties of three tetragonal prismatic cages 4a-4c constructed from eight 90o Pt(II) acceptors, four linear dipyridyl ligands and two tetraphenylethene (TPE) based sodium benzoate ligands are described. These cages are emissive in dilute solutions due to the metal-coordination induced partial restriction of intramolecular rotation of their TPE units, while the dipyridyl moieties which act as the pillars as well as the solvents strongly influence these emissions. Specifically, cages 4a and 4b bearing a 4,4'dipyridine and a 1,2-di(4-pyridyl)ethylene as their pillar parts, respectively, display good emissions in common organic solvents at 485~493 nm that are derived from the TPE units. 1

ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Whereas, cage 4c with its BODIPY-based dipyridyl unit exhibits two emission bands at 462~473 nm and 540~545 nm, originating from the TPE and BODIPY fluorophores, respectively. Moreover, cage 4b has been employed as a turn-on fluorescent sensor for thiol-containing amino acids via a self-destructive reaction. While the cage can also be regenerated via the addition of Pt(II) acceptors. The studies described herein not only enrich the ongoing research on fluorescent materials but also pave the way to prepare stimuli-responsive supramolecular coordination complexes.

■ INTRODUCTION Light-emitting materials with tunable fluorescence properties are of interest due to their wide ranging applications as chemical sensors, biological labels, organic light emitting diodes and so on.1 The covalent preparation of such materials often requires tedious and time-consuming chemical synthesis.2 In contrast, constructions via supramolecular chemistry, in particular metalcoordination driven self-assembly3 benefit from fewer synthetic steps and afford highly diverse supramolecular coordination complexes (SCCs)4-6 with interesting photophysical properties. The well-defined geometry of these metallo-supramolecular structures provides precise control over the numbers, locations and relative orientations of the chromophores in these highly concentrated chromophoric ensembles. Moreover, the interplay between the metal and ligand precursors sometimes endows the final constructs with unique properties which are not possessed by the individual components. For example, we reported a series of Pt(II)←pyridine coordination based rhomboidal metallacycles that exhibited far red shifted (ca. 80~100 nm) emissions in the visible region compared to the corresponding ligands.5a At the same time, the emission wavelengths of these supramolecular constructs can be tuned by modulating the electron density of their donor 2


Page 2 of 23

Page 3 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


building blocks. Lusby et al. prepared an Ir6L4 octahedral cage with luminescent properties, though the mononuclear metal complex itself is non-emissive.7 Nitschke and coworkers observed that the incorporation of multiple fluorophores into Fe(II)-based M4L6 cages can allow the detection of anions as well as provide white-light emission.8 However, at times the emissions of SCCs were significantly quenched either by the heavy atom effect of the transition metal ions or via intramolecular charge transfer process,9 suggesting that only an appropriate selection of building blocks can allow the construction of highly emissive SCCs. Tetraarylethylene derivatives are a class of specific fluorophores that are non-emissive in dilute solution but exhibit strong fluorescence in the aggregated state due to the restriction of molecular rotation of the aryl groups.10 This effect is termed as the aggregation induced emission (AIE) by Tang and coworkers.10 Previously, we observed that the immobilization of TPE-based pyridyl ligands in metallo-supramolecular structures plays a similar role in limiting their molecular rotations, thereby furnishing highly emissive SCCs.6a Herein, we further explore this phenomenon and describe the preparation of three emissive tetragonal prismatic metallacages 4a, 4b and 4c consisting of eight 90o Pt(II) acceptors, four dipyridyl ligands and two sodium benzoate-decorated TPE units. Notably, the emission properties of these metallacages can be finely tuned by the variation of the dipyridyl ligands as well as the solvents. Cages 4a and 4b, with 4,4'-dipyridine and 1,2-dipyridylethene units as the pillars, respectively, show good emission at 485~494 nm in a wide range of solvents such as DMSO, acetonitrile, acetone, dichloromethane, etc. At the same time, the presence of a 4,4-difluoro-4-bora-3a,4a-diaza-sindacene (BODIPY) dipyridyl derivative (3c) as the pillars endows the cage 4c with two distinct emission bands at 462~475 nm and 540~545 nm, wherein the former displays the emission characteristics of the TPE units and the latter originates from the BODIPY fluorophores. 3



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Cage 4b is non-emissive in methanol/water (1/1, v/v), while the same solution strongly emits when thiol-containing amino acids, for instance cysteine and glutathione, were added. This allows the fluorescence sensing of these amino acids. The sensing follows a self-destructive mechanism, in which the cage is decomposed to give the TPE-based precursor which exhibits strong fluorescence in the same solvent mixture due to an AIE effect.10 Additionally, the cage was regenerated via the addition of Pt(II) acceptors, representing a novel way to create stimuliresponsive SCCs.

■ RESULTS AND DISCUSSION Cage preparation and characterization

Cages 4a-4c (Figure 1a) were prepared in greater than 90% isolated yields by adopting a literature procedure,11 as outlined in the experimental section. The formation of these cages was established by multinuclear NMR (1H NMR and

31

P{1H} NMR), electrospray ionization

time‒of‒flight mass (ESI‒TOF‒MS), UV−Vis and fluorescence spectroscopies. For instance, the 31

P{1H} NMR spectra (Figure 1, spectra c–e) exhibit two doublets of equal intensity with

concomitant 195Pt satellites at 1.04 and –4.50 ppm for 4a, 1.09 and –4.38 ppm for 4b, 0.89 and – 4.54 ppm for 4c, supporting the formation of these discrete, charge-separated metallacages.11 In the 1H NMR spectra of 4a, significant downfield shifts were observed for H1 (from 8.72 ppm to 8.90 ppm) and H2 (from 7.57 ppm to 8.03 ppm) (Figure 1, spectra f and g) as compared to the free pyridine ligand 3a, due to the coordination of the pyridyl units to the Pt(II) ions.11 Similar downfield shifts from the ligand 3b were also observed for the pyridyl protons H3 (from 8.61 ppm to 8.68 ppm) and H4 (from 7.42 ppm to 7.72 ppm) as well as ethylene protons H5 (from 7.26 4


Page 4 of 23

Page 5 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


ppm to 7.44 ppm) of 4b (Figure 1, spectra h and i). In the proton NMR spectrum of 4c, signals for the pyridyl protons H6 (from 8.62 ppm to 8.65 ppm) and H7 (from 7.14 ppm to 7.17 ppm) displayed the downfield shifts, as expected, whereas the aromatic protons H10 (from 7.37 ppm to 6.84 ppm) and H11 (from 7.26 ppm to 6.84 ppm) and the methyl protons H8 (from 1.40 ppm to 0.82 ppm), H9 (from 2.54 ppm to 2.14 ppm) and H12 (from 2.45 ppm to 2.41 ppm) shifted upfield (Figure 1, spectra j and k), likely due to the cage structure. ESI-TOF-MS, supports the putative stoichiometry (Figure 1) of these metallacages by showing isotopically well-resolved peaks at m/z = 2145.06, 2179.65 and 2591.76 (Figure 2), corresponding to the [M – 3OTf]3+ species of 4a-4c, respectively (where M= intact assembly).

5



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

6


Page 6 of 23

Page 7 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 1. (a) Synthetic routes and cartoon representations of cages 4a, 4b and 4c.

31

P{1H} (b˗e) and

partial 1H NMR (f-k) spectra (121.4 MHz or 400 MHz, CD2Cl2, 293 K) of 2 (b), 4a (c and g), 4b (d and i), 4c (e and k), 3a (f), 3b (h), 3c (j).

Figure 2. Experimental (red) and calculated (blue) ESI-TOF-MS spectra of 4a [M – 3OTf]3+ (a), 4b [M – 3OTf]3+ (b) and 4c [M – 3OTf]3+ (c).

Figure 3. Simulated molecular models of 4a (a), 4b (b) and 4c (c) optimized by PM6 semiempirical molecular orbital methods. The hydrogen atoms and ethyl groups of the PEt3 were omitted for clarity.

Molecular simulations (Figure 3) were performed to get further information about the structures of the metallacages 4a, 4b and 4c. All three cages are tetragonal prism structures 7



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

where the TPE units, dipyridyl moieties and 90o Pt(II) ions construct the faces, the pillars and the corners, respectively. Using the distance between the Pt(II) centers, the length, width and diameter for cages 4a-4c are computed as ca. 2.00 nm, 1.75 nm and 3.80 nm, respectively. However, the height of these cages is different as expected, cage 4c has a higher value (1.94 nm) compared to that of the cages 4a (1.12 nm) and 4b (1.34 nm).

Photophysical studies

These cages are stable in a series of solvents (Figure S15), including even some coordinating solvents like acetonitrile, DMSO, etc. This allows us to probe their photophysical properties in a wide range of solvents as shown in Figure 4. In dichloromethane, cage 4a has a broad absorption band at 282 nm and two shoulders at 320 nm and 361 nm with molar absorption coefficients (ε) of 1.26 × 105, 7.41 × 104 and 2.60 × 104 M-1cm-1, respectively (Figure 4a). Cage 4b shows a sharp absorption peak centered at 318 nm and two shoulders at 335 nm and 368 nm with ε of 2.09 × 105, 1.27 × 105 and 6.51 × 104 M-1cm-1, respectively (Figure 4c), while two broad absorption bands at 278 nm and 319 nm and a sharp absorption peak at 520 nm with ε of 1.42 × 105, 1.09 × 105 and 2.51× 105 M-1cm-1, respectively (Figure 4e), was observed for 4c in the same solvent. The UV-Vis spectra of these cages in six other solvents, as shown in Figure 4, are similar to that of their dichloromethane solution, suggesting that these solvents have negligible influence on the absorbance properties.12 We suppose that the absorption bands in the range of 350~370 nm result from the TPE derivatives,10 while the strong absorption of the BODIPY chromophore in cage 4c is characterized by the peak at 520 nm.13

8


Page 8 of 23

Page 9 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 4. The UV/Vis absorption12 (a, c, e) and fluorescence (b, d, f) spectra of cages 4a (a, b), 4b (c, d) and 4c (e, f) in different solvents (λex = 365 nm, c = 10.0 µM).

9



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 23

Table 1. Emission data of cages 4a, 4b and 4c in different solvents. 4a

4b

4c

Solvents

λem, nm

ΦF (%)

λem, nm

ΦF (%)

λem, nm

ΦF (%)

DMSO

493

25.8

492

19.1

473, 545

13.9

DMF

494

24.3

493

21.4

475, 544

12.2

Acetonitrile

491

24.7

493

18.7

472, 540

11.9

Acetone

488

11.1

490

7.10

469, 541

9.62

Methanol

488

1.37

491

0.93

470, 540

3.09

Dichloromethane

491

0.61

490

0.16

462, 543

4.46

Chloroform

489

0.91

485

0.63

472, 543

2.47

Since the TPE groups are partially rigidified in these cages and the rotation of their aromatic rings is limited by the metal-coordination bonds, we anticipated that these structural characteristics endow the cages with good fluorescence properties. The emission spectra of the cages in seven different solvents are shown in Figure 4. In polar aprotic solvents such as DMSO, DMF and acetonitrile, cages 4a and 4b show strong emission at around 493 nm, due to the emission of the TPE groups.10 Cage 4c exhibits two strong emission peaks at around 472 nm and 544 nm, due to the emission of both the TPE10 and BODIPY13 groups, respectively. In less polar aprotic solvents including acetone, dichloromethane and chloroform, as well as polar protic solvent, such as methanol, these cages show only moderate emissions. The quantum yields (ΦF) of 4a-4c (Table 1) were also determined in different solvents: in polar aprotic solvents, the ΦF values of 4a, 4b and 4c were 25%, 20% and 13%, respectively, and represent the highest values among all of the solvents. These data suggest that the emission wavelengths of these cages depend largely upon their dipyridyl ligands, while their quantum yields can be finely tuned by the variation of solvents. 10


Page 11 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


We also sought to rigidify the cages by the encapsulation of a guest as this might further enhance their emissions. Consequently, we studied the host-guest chemistry of these cages using anthracene and pyrene as the guests. However, no host-guest complexes either in pure acetone or in an acetone/water mixture were observed (see Figure S16).

Thiol-containing Amino Acid Recognition

Given the strong binding affinity of thiols to Pt(II) ions,14 we explored the use of cage 4b as a turn-on sensor for thiol-containing amino acids, which are crucial functional groups in biology.15 After examining a series of solvent compositions we chose a methanol/water (1/1, v/v) mixture for the chemo-sensing because in this medium the cage is nearly non-emissive (Figure S17), which makes it an ideal candidate for “Turn On” fluorescence sensing.16 The emissions of the other two cages are not fully quenched in this medium, indicating that the pillars likely have an influence on the quenching.10

Time dependent fluorescence spectra of 4b (10 µM) with 1 mM glutathione (Figure S18) were collected in methanol/water (1/1, v/v): as the reaction proceeded, the emission at 500 nm increased and reached a maximum value after 5 min, indicating that the system reached its equilibrium state at this point. Next, we studied the interactions of cage 4b with thiol-containing amino acids (glutathione and cysteine) by fluorescence titration experiments (Figure 5). Upon the gradual addition of the amino acids into a solution of 4b (10 µM), the fluorescence emission intensity at 500 nm dramatically increased in the concentration range of 2 µM to 80 µM, while only a small increase was observed when the concentration exceeds 120 µM (Figure 5). The 11



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 23

fluorescence intensity is linearly proportional to the concentration of the amino acids in the 0–80 µM range (Figure 5b), indicating that cage 4b is suitable for quantitative detection of these amino acids. The detection limits for glutathione and cysteine are 1.89 × 10-7 M and 2.78 × 10-7 M (S/N = 3), respectively. Control experiments were performed using other amino acids such as glycine, alanine, arginine, lysine, serine, leucine, isoleucine, glutamate and histidine which show negligible emission enhancement (Figure S20). These data suggest that 4b can be considered as a turn-on sensor for thiol-containing amino acids.

Figure 5. Fluorescence spectra of cage 4b (10 µM) after 5 min upon the addition of increasing concentrations of glutathione (a) and cysteine (c) and the emission intensities at 500 nm as a function of glutathione (b) and cysteine (d) concentration. Each spectrum was collected in methanol/water (1/1, v/v) 12


Page 13 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


with λex = 365 nm. Inset: photograph of 10 µM cage 4b before (left) and after (right) the addition of 160 µM thiol-containing amino acids in methanol/water (1/1, v/v) upon excitation at 365 nm using a UV lamp at 298 K.

To understand the mechanism of the above sensing, 1H NMR titration experiments were performed (Figures 6, S22-S27) by gradually adding cysteine or glutathione to a DMSO-solution of cage 4b. After the addition of 2 equiv. of the amino acids respectively with regard to the initial amount of the cage, the diagnostic α and β pyridyl protons H3 and H4 of 4b split into two sets, in which the set corresponding to the cage was present as the major amount, while the minor set appeared in a region similar to that of the free ligand 3b, suggesting that these amino acids can decompose the cage and release its precursors. This minor set of peaks gradually increased in amount as the titration advanced, and became the major set in the presence of 6 equiv. of the amino acids. Moreover, the 1H NMR spectrum of cage 4b along with 8 equiv. of amino acid (Figure 6f) equals the sum of the individual spectra of 3b (Figure 6g) and 5 (Figure 6h), indicating that the cage is now totally destroyed. This destruction was also confirmed by the corresponding

31

P{1H} NMR spectrum in which the two characteristic doublet peaks of 4b

disappeared (Figure S24). The complexation between Pt(PEt3)2(OTf)2 and the amino acids was also investigated by 1H NMR (Figures S28 and S29) and ESI-TOF-MS spectroscopies (Figures S30 and S31), suggesting a 1:1 binding stoichiometry between Pt(PEt3)2(OTf)2 and the respective amino acids.

The cage was regenerated by the addition of Pt(II) acceptors (Figure S32),

suggesting that the thermodynamic stability of the Pt-amino acids complexes are more than that of the cage. The addition of 2-mercaptoethanol into the solution of 4b provides further information for the formation of complex between Pt(II) and amino acids. The cage remains stable even when 100 equiv. of 2-mercaptoethanol was added (Figure S33), indicating that both 13



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

the thiol group and the carboxylic group act as coordinative ligands with Pt(II). We also prepared compound 5 and recorded its emission spectrum in methanol/water (1/1, v/v) mixture (Figure S34). The data suggests that it is emissive in this medium because of the AIE effect. Based on these data, we propose a self-destructive mechanism (Figure 6a) for the sensing. Specifically, the amino acids act as better ligands for the Pt(II) ions, leading to the destruction of the cage as well as formation of mononuclear Pt(II)-amino acid complexes. This then releases the emissive ligand 5, which acts as the indicator in the sensing of the thiol-containing amino acids.

14


Page 14 of 23

Page 15 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 6. Cartoon representation of the self-destructive mechanism (a). Partial 1H NMR (400 MHz, CD3SOCD3, 293 K) of 1.0 mM cage 4b (b) by the addition of 2.0 mM (c), 4.0 mM (d), 6.0 mM (e) and 8.0 mM (f) cysteine; 5 (g) and 3b (h).

15



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 23

■ CONCLUSION In summary, we have prepared and spectroscopically characterized three different tetragonal prismatic Pt(II) metallacages 4a-4c, which contain two benzoate-TPE groups as the faces, four dipyridyl ligands as the pillars and eight 90o Pt(II) acceptors as the corners. Due to the metalcoordination induced partial restriction of intramolecular rotations of their TPE units these cages are emissive. The emission properties could be further tuned by different dipyridyl ligands as well as by the solvents. Furthermore, a self-destructive mechanism was demonstrated for the thiol-containing amino acid sensing properties by cage 4b in methanol/water (1/1, v/v). These emissive metallacages not only provide new types of emissive materials with tunable emission properties but also give insights into the stimuli-responsive destruction of these cages, making them potential candidates for light-emitting materials, chemosensors and smart drug delivery systems.

■ EXPERIMENTAL SECTION Materials and Methods. All reagents were commercially available and used as supplied without further purification. Deuterated solvents were purchased from Cambridge Isotope Laboratory (Andover, MA). 1,3,5,7-tetramethyl-2,6-diiodide-8-p-methylbenzene-BODIPY,17 1,18 and 219 were prepared according to the literature procedures. NMR spectra were recorded on a Varian Unity 300 MHz or 400 MHz spectrometer. 1H and 13C NMR chemical shifts are reported relative to residual solvent signals, and

31

P{1H} NMR chemical shifts are referenced to an external

unlocked sample of 85% H3PO4 (δ = 0.0). Mass spectra were recorded on a Micromass Quattro II triple-quadrupole mass spectrometer using electrospray ionization with a MassLynx operating system. The UV-vis experiments were conducted on a Hitachi U-4100 absorption 16


Page 17 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


spectrophotometer. The fluorescent experiments were conducted on a Hitachi F-7000 fluorescence spectrophotometer. Quantum yields were determined using quinine sulfate at 365 nm (ΦF = 56%). The quantum yields were calculated from comparisons of the integrated signals of the excitation and emission signals using the FluorEssence software package (Horiba). Synthesis of 3c. To 1,3,5,7-tetramethyl-2,6-diiodide-8-p-methylbenzene-BODIPY (296 mg, 0.5 mmol), 4pyridylboronic acid (184 mg, 1.5 mmol) in toluene (40 mL), aqueous K2CO3 (207 mg, 1.5 mmol) solution (10 mL) and ethanol (10 mL) were added. Then Pd(PPh3)4 (69 mg, 0.06 mmol) was added and the reaction mixture was stirred at 80 °C for 48 h under nitrogen atmosphere. After cooling to room temperature, the product was concentrated and purified by flash column chromatography with CH2Cl2:CH3OH (70:1, v/v) as the eluent to afford compound 5c (136 mg, 55%) as red powder. 1H NMR (400 MHz, CD2Cl2, 295K): 8.62 (d, J = 5.8 Hz, 4H), 7.37 (d, J = 7.9 Hz, 2H), 7.26 (d, J = 7.9 Hz, 2H), 7.14 (d, J = 5.8 Hz, 4H), 2.54 (s, 6H), 2.45 (s, 3H), 1.40 (s, 6H). 13C NMR (100 MHz, CD2Cl2, 295K): 153.8, 149.8, 141.6, 140.1, 139.6, 131.6, 130.1, 127.6, 124.9, 21.1, 13.1, 12.6. HR-MS: m/z 493.2373 ([3c + H]+, calcd. for [C30H28BF2N4]+, 493.2375. Self-assembly of 4a. 1 (2.25 mg, 2.50 µmol), 2 (7.30 mg, 10.0 µmol) and 3a (0.78 mg, 5.00 µmol) were mixed in a 1:4:2 molar ratio and dissolved in acetone/water (1.0 mL, 4:1, v/v). The whole reaction mixture was heated at 50 oC for 12 h and then cooled to room temperature. The solvent was removed by nitrogen flow. The residue was redissolved in acetone (1.0 mL), filtered and the filtrate was poured into ethyl ether (10 mL) to give a precipitate, which was collected by centrifugation to give 4a (8.43 mg, 98%) as a pale yellow powder. 1H NMR (400 MHz, CD2Cl2, 295 K): 8.90 (d, J = 6.6 Hz, 16H), 8.03 (d, J = 6.6 Hz, 16H), 7.79 (d, J = 8.3 Hz, 16H), 7.42 (d, J = 8.3 Hz, 16H), 7.25 (d, J = 8.3 Hz, 16H), 7.07 (d, J = 8.3 Hz, 16H), 1.65–2.05 (m 96H), 1.13–1.40 (m, 144H). 31P{1H} NMR (CD2Cl2, 295 K, 121.4 MHz) δ (ppm): 1.04 ppm (d, 2JP–P = 21.4 Hz, 195Pt satellites, 1JPt–P = 3402 Hz), –4.50 ppm (d, 2JP–P = 21.4 Hz, 195Pt satellites, 1JPt–P = 3402 Hz). ESI-TOF-MS: m/z 1572.17 [4a – 4OTf]4+, 2145.06 [4a – 3OTf]3+.

17



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 23

Self-assembly of 4b. 1 (2.25 mg, 2.50 µmol), 2 (7.30 mg, 10.0 µmol) and 3b (0.91 mg, 5.00 µmol) were mixed in a 1:4:2 molar ratio and dissolved in acetone/water (1.0 mL, 4:1, v/v). The whole reaction mixture was heated at 50 oC for 12 h and then cooled to room temperature. The solvent was removed by nitrogen flow. The residue was redissolved in acetone (1.0 mL), filtered and the filtrate was poured into ethyl ether (10 mL) to give a precipitate, which was collected by centrifugation to give 4b (8.30 mg, 95%) as a pale yellow powder. The sample was dissolved in CD2Cl2 for characterization. 1H NMR (400 MHz, CD2Cl2, 295 K): 8.66–8.72 (m, 16H), 7.70–7.78 (m, 32H), 7.44 (s, 8H), 7.43 (d, J = 8.3 Hz, 16H), 7.30 (d, J = 8.3 Hz, 16H), 7.10 (d, J = 8.3 Hz, 16H), 1.70–2.05 (m, 96H), 1.15–1.36 (m, 144H). 31P{1H} NMR (CD2Cl2, 295 K, 121.4 MHz) δ (ppm): 1.09 ppm (d, 2JP–P = 21.2 Hz, 195Pt satellites, 1JPt–P = 3420 Hz), –4.38 ppm (d, 2JP–P = 21.2 Hz, 195Pt satellites, 1JPt–P = 3420 Hz). ESI-TOF-MS: m/z 1595.37 [4b – 4OTf]4+, 2179.65 [4b – 3OTf]3+. Self-assembly of 4c. 1 (2.25 mg, 2.50 µmol), 2 (7.30 mg, 10.0 µmol) and 3c (2.47 mg, 5.00 µmol) were mixed in a 1:4:2 molar ratio and dissolved in acetone/water (1.0 mL, 4:1, v/v). The whole reaction mixture was heated at 50 oC for 12 h and then cooled to room temperature. The solvent was removed by nitrogen flow. The residue was redissolved in acetone (1.0 mL), filtered and the filtrate was poured into ethyl ether (10 mL) to give a precipitate, which was collected by centrifugation to give 4c (9.47 mg, 92%) as a red powder. The sample was dissolved in CD2Cl2 for characterization. 1H NMR (400 MHz, CD2Cl2, 295 K): 8.61–8.70 (m, 16H), 7.58 (d, J = 8.3 Hz, 16H), 7.24–7.35 (m, 48H), 7.17 (d, J = 5.8 Hz, 16H), 6.83–6.87 (m, 16H), 2.41 (s, 12H), 2.14 (s, 24H), , 1.70–2.05 (m, 96H), 1.10–1.40 (m, 144H), 0.81 (s, 24H).

31

P{1H} NMR (CD2Cl2, 295 K, 121.4 MHz) δ (ppm): 0.89 ppm (d, 2JP–P = 19.2 Hz,

195

Pt

satellites, 1JPt–P = 3440 Hz), –4.54 (d, 2JP–P = 19.2 Hz, 195Pt satellites, 1JPt–P = 3440 Hz). ESI-TOF-MS: m/z 1907.91 [4c – 4OTf]4+, 2591.76 [4c – 3OTf]3+.

■ ASSOCIATED CONTENT Supporting Information 18


Page 19 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


The supporting information is available free of charge via the Internet at http://pubs.acs.org. Syntheses and characterization data (NMR, ESI-TOF-MS, Fluorescence Spectra), including Figures S1−S34.

■ AUTHOR INFORMATION Corresponding Author [email protected]; [email protected]; [email protected]; [email protected] Notes The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS P.J.S. thanks National Science Foundation (Grant 1212799) for financial support. F.H. and P.J.S. thank National Natural Science Foundation of China (21620102006) for financial support. X.L. thanks the National Science Foundation (CHE-1506722) and PREM Center of Texas State University (DMR-1205670) for financial support. S.Y. thanks National Natural Science Foundation of China (21574034, 21274034) and Zhejiang Provincial Natural Science Foundation of China (LY16B040006) for financial support. Computational resources are gratefully acknowledged from the Center for High Performance Computing (CHPC) at the University of Utah.

■REFERENCES (1) (a) Bessette, A.; Hanan, G. S. Chem. Soc. Rev. 2014, 43, 3342. (b) Lo, K. K. Acc. Chem. Res. 2015, 48, 2985. (c) Staderini, M.; Antonia Martin, M.; Bolognesi, M. L.; Carlos Menendez, J. Chem. Soc. Rev. 2015, 44, 1807. (d) Yang, X.; Zhou, G.; Wong, W. Y. Chem. Soc. Rev. 2015, 44, 8484. (e) Yam, V. W.; Au, V. K.; Leung, S. Y. Chem. Rev. 2015, 115, 7589. (f) 19



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 23

Kobayashi, M.; Hayakawa, N.; Matsuo, T.; Li, B.; Fukunaga, T.; Hashizume, D.; Fueno, H.; Tanaka, K.; Tamao, K. J. Am. Chem. Soc. 2016, 138, 758. (2) (a) Qian, J.; Zhu, Z.; Qin, A.; Qin, W.; Chu, L.; Cai, F.; Zhang, H.; Wu, Q.; Hu, R.; Tang, B. Z.; He, S. Adv. Mater. 2015, 27, 2332. (b) Poon, C. T.; Wu, D.; Yam, V. W. Angew. Chem. Int. Ed. 2016, 55, 3647. (c) Zeng, L.; Liu, T.; He, C.; Shi, D.; Zhang, F.; Duan, C. J. Am. Chem. Soc. 2016, 138, 3958. (d) Kortekaas, L.; Ivashenko, O.; van Herpt, J. T.; Browne, W. R. J. Am. Chem. Soc. 2016, 138, 1301. (e) Chowdhury, A.; Howlader, P.; Mukherjee, P. S. Chem. – Eur. J. 2016, 22, 7468. (3) (a) Inokuma, Y.; Kawano, M.; Fujita, M. Nat. Chem. 2011, 3, 349. (b) Lee, C. Y.; Farha, O. K.; Hong, B. J.; Sarjeant, A. A.; Nguyen, S. T.; Hupp, J. T. J. Am. Chem. Soc. 2011, 133, 15858. (c) Sun, B.; Wang, M.; Lou, Z.; Huang, M.; Xu, C.; Li, X.; Chen, L. J.; Yu, Y.; Davis, G. L.; Xu, B.; Yang, H. B.; Li, X. J. Am. Chem. Soc. 2015, 137, 1556. (d) Kaphan, D. M.; Toste, F. D.; Bergman, R. G.; Raymond, K. N. J. Am. Chem. Soc. 2015, 137, 9202. (e) Wang, Q. Q.; Gonell, S.; Leenders, S. H.; Durr, M.; Ivanovic-Burmazovic, I.; Reek, J. N. Nat. Chem. 2016, 8, 225. (f) Jiang, B.; Zhang, J.; Ma, J. Q.; Zheng, W.; Chen, L. J.; Sun, B.; Li, C.; Hu, B.; Tan, H.; Li, X.; Yang, H. B. J. Am. Chem. Soc. 2016, 138, 738. (g) Howlader, P.; Das, P.; Zangrando, E.; Mukherjee, P. S. J. Am. Chem. Soc. 2016, 138, 1668. (h) Wang, M.; Wang, K.; Wang, C.; Huang, M.; Hao, X. Q.; Shen, M. Z.; Shi, G. Q.; Zhang, Z.; Song, B.; Cisneros, A.; Song, M. P.; Xu, B.; Li, X. J. Am. Chem. Soc. 2016, 138, 9258. (4) (a) Stang, P. J.; Olenyuk, B. Acc. Chem. Res. 1997, 30, 502. (b) Leininger, S.; Olenyuk, B.; Stang, P. J. Chem. Rev. 2000, 100, 853. (c) Fujita, M.; Tominaga, M.; Hori, A.; Therrien, B. Acc. Chem. Res. 2005, 38, 369. (d) Oliveri, C. G.; Ulmann, P. A.; Wiester, M. J.; Mirkin, C. A. Acc. Chem. Res. 2008, 41, 1618. (e) Northrop, B. H.; Zheng, Y.-R.; Chi, K.-W.; Stang, P. 20


Page 21 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


J. Acc. Chem. Res. 2009, 42, 1554. (f) De, S.; Mahata, K.; Schmittel, M. Chem. Soc. Rev. 2010, 39, 1555. (g) Chakrabarty, R.; Mukherjee, P. S.; Stang, P. J. Chem. Rev. 2011, 111, 6810. (h) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T. Chem. Rev. 2012, 112, 1105. (i) Cook, T. R.; Zheng, Y.-R.; Stang, P. J. Chem. Rev. 2013, 113, 734. (j) Nakamura, T.; Ube, H.; Shiro, M.; Shionoya, M. Angew. Chem., Int. Ed. 2013, 52, 720. (k) Brown, C. J.; Toste, F. D.; Bergman, R. G.; Raymond, K. N. Chem. Rev. 2015, 115, 3012. (l) Cook, T. R.; Stang, P. J. Chem. Rev. 2015, 115, 7011. (m) Newkome, G. R.; Moorefield, C. N. Chem. Soc. Rev. 2015, 44, 3954. (n) McConnell, A. J.; Wood, C. S.; Neelakandan, P. P.; Nitschke, J. R. Chem. Rev. 2015, 115, 7729. (5) (a) Pollock, J. B.; Schneider, G. L.; Cook, T. R.; Davies, A. S.; Stang, P. J. J. Am. Chem. Soc. 2013, 135, 13676. (b) Chen, L. J.; Ren, Y. Y.; Wu, N. W.; Sun, B.; Ma, J. Q.; Zhang, L.; Tan, H.; Liu, M.; Li, X.; Yang, H. B. J. Am. Chem. Soc. 2015, 137, 11725. (c) Yan, X.; Wang, H.; Hauke, C. E.; Cook, T. R.; Wang, M.; Saha, M. L.; Zhou, Z.; Zhang, M.; Li, X.; Huang, F.; Stang, P. J. J. Am. Chem. Soc. 2015, 137, 15276. (d) Chowdhury, A.; Howlader, P.; Mukherjee, P. S. Chem. – Eur. J. 2016, 22, 1424. (e) Zhang, M.; Li, S.; Yan, X.; Zhou, Z.; Saha, M. L.; Wang, Y. C.; Stang, P. J. Proc. Natl. Acad. Sci. USA 2016, 113, 11100. (f) Zhang, M.; Yin, S.; Zhang, J.; Zhou, Z.; Saha, M. L.; Lu, C.; Stang, P. J. Proc. Natl. Acad. Sci. USA 2017, 114, 3044. (6) (a) Yan, X.; Cook, T. R.; Wang, P.; Huang, F.; Stang, P. J. Nat. Chem. 2015, 7, 342. (b) Yamashina, M.; Sartin, M. M.; Sei, Y.; Akita, M.; Takeuchi, S.; Tahara, T.; Yoshizawa, M. J. Am. Chem. Soc. 2015, 137, 9266. (c) Yan, X.; Wang, M.; Cook, T. R.; Zhang, M.; Saha, M. L.; Zhou, Z.; Li, X.; Huang, F.; Stang, P. J. J. Am. Chem. Soc. 2016, 138, 4580. (d) Saha, M. L.; Yan, X.; Stang, P. J. Acc. Chem. Res. 2016, 49, 2527. 21



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 23

(7) Chepelin, O.; Ujma, J.; Wu, X.; Slawin, A. M.; Pitak, M. B.; Coles, S. J.; Michel, J.; Jones, A. C.; Barran, P. E.; Lusby, P. J. J. Am. Chem. Soc. 2012, 134, 19334. (8) Neelakandan, P. P.; Jimenez, A.; Nitschke, J. R. Chem. Sci. 2014, 5, 908. (9) (a) Wasielewski, M. R. Chem. Rev. 1992, 92, 435. (b) Daly, B.; Ling, J.; de Silva, A. P. Chem. Soc. Rev. 2015, 44, 4203. (10)

(a) Zhao, Z.; Lam, J. W. Y.; Tang, B. Z. J. Mater. Chem. 2012, 22, 23726. (b) Mei, J.;

Hong, Y.; Lam, J. W. Y.; Qin, A.; Tang, Y.; Tang, B. Z. Adv. Mater. 2014, 26, 5429. (c) Mei, J.; Leung, N. L.; Kwok, R. T.; Lam, J. W.; Tang, B. Z. Chem. Rev. 2015, 15, 11718. (11)

(a) Wang, M.; Zheng, Y.-R.; Ghosh, K.; Stang, P. J. J. Am. Chem. Soc. 2010, 132, 6282.

(b) Zheng, Y.-R.; Zhao, Z.; Wang, M.; Ghosh, K.; Pollock, J. B.; Cook, T. R.; Stang, P. J. J. Am. Chem. Soc. 2010, 132, 16873. (c) Zheng, Y.-R.; Lan, W.-J.; Wang, M.; Cook, T. R.; Stang, P. J. J. Am. Chem. Soc. 2011, 133, 17045. (d) Zhang, M.; Saha, M. L.; Stang, P. J. Struct. Chem. 2016, 28, 453. (12)

The sharp drop at 320 nm is due to an artefact from acetone, because the UV cut-off

wavelength of the solvent is much longer (330~340 nm) compared to the other solvents. (13)

Boens, N.; Leen, V.; Dehaen, W. Chem. Soc. Rev. 2012, 41, 1130.

(14)

(a) Machan, C. W.; Adelhardt, M.; Sarjeant, A. A.; Stern, C. L.; Sutter, J.; Meyer, K.;

Mirkin, C. A. J. Am. Chem. Soc. 2012, 134, 16921. (b) Mendez-Arroyo, J.; Barroso-Flores, J.; Lifschitz, A. M.; Sarjeant, A. A.; Stern, C. L.; Mirkin, C. A. J. Am. Chem. Soc. 2014, 136, 10340. (c) Lifschitz, A. M.; Rosen, M. S.; McGuirk, C. M.; Mirkin, C. A. J. Am. Chem. Soc. 2015, 137, 7252. (15)

(a) Niu, L.-Y.; Guan, Y.-S.; Chen, Y.-Z.; Wu, L.-Z.; Tung, C.-H.; Yang, Q.-Z. J. Am.

Chem. Soc. 2012, 134, 18928. (b) Liu, J.; Sun, Y. Q.; Huo, Y.; Zhang, H.; Wang, L.; Zhang, 22


Page 23 of 23

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


P.; Song, D.; Shi, Y.; Guo, W. J. Am. Chem. Soc. 2014, 136, 574. (c) Niu, L. Y.; Chen, Y. Z.; Zheng, H. R.; Wu, L. Z.; Tung, C. H.; Yang, Q. Z. Chem. Soc. Rev. 2015, 44, 6143. (16)

We have also performed the amino acid sensing study in methanol/water (1/9, v/v)

mixture and the corresponding fluorescence spectra are shown in Figure S21. (17)

Ye, J.-H.; Hu, Z.; Wang, Y.; Zhang, W.; Zhang, Y. Tetrahedron Lett. 2012, 53, 6858.

(18)

Zhang, Q.; Su, J.; Feng, D.; Wei, Z.; Zou, X.; Zhou, H. C. J. Am. Chem. Soc. 2015, 137,

10064. (19)

Stang, P. J.; Cao, D. H.; Saito, S.; Arif, A. M. J. Am. Chem. Soc. 1995, 117, 6273.

TOC Graphic:

23


Multicomponent Platinum(II) Cages with Tunable ... - ACS Publications

Recommend Documents